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Compendium of Organic Synthetic Methods

Compendium of Organic Synthetic Methods

Compendium of Organic Synthetic Methods Volume 9 MICHAEL

B. SMITH

DEPARTMENT OF CHEMISTRY THE UNIVERSITY OF CONNECTICUT STORRS, CONNECTICUT

A Wiley-Interscience

Publication

JOHN WILEY & SONS, INC. New York

l

Chichester

l

Weinheim

l

Brisbane

l

Sinaar>ore

l

Toronto

Copyright  2001 by John Wiley and Sons, Inc., New York. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic or mechanical, including uploading, downloading, printing, decompiling, recording or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without the prior written permission of the Publisher. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-Mail: PERMREQ @ WILEY.COM. This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold with the understanding that the publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional person should be sought. ISBN 0-471-22822-2. This title is also available in print as ISBN 0-471-14579-3. For more information about Wiley products, visit our web site at www.Wiley.com.

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

CONTENTS PREFACE ABBREVIATIONS INDEX, MONOFUNCTIONAL COMPOUNDS INDEX, DIFUNCTIONAL COMPOUNDS INTRODUCTION PREPARATION OF ALKYNES PREPARATION OF ACID DERIVATIVES PREPARATION OF ALCOHOLS PREPARATON OF ALDEHYDES PREPARATION OF ALKYLS, METHYLENES AND ARYLS PREPARATION OF AMIDES PREPARATION OF AMINES PREPARATION OF ESTERS PREPARATION OF ETHERS, EPOXIDES AND THIOETHERS 10 PREPARATION OF HALIDES AND SULFONATES 11 PREPARATION OF HYDRIDES 12 PREPARATION OF KETONES 13 PREPARATION OF NITRILES 14 PREPARATION OF ALKENES 15 PREPARATION OF OXIDES 16 PREPARATION OF DIFUNCTIONAL COMPOUNDS AUTHOR INDEX

vii ix … XIII

xv

1 5 11 48 58 100 117 140 156 171 176 183 208 212 227 235 391

PREFACE Since the original volume in this series by Ian and Shuyen Harrison, the goal of the Compendium of Organic Synthetic Methods was to facilitate the search for functional group transformations in the original Iiterrature of Organic Chemistry. In Volume 2, difunctional compounds were added and this compilation was continued by Louis Hegedus and Leroy Wade for Voume 3 of the series. Wade became the author for Volume 4 and continued with Volume 5. I began editing the series with Volume 6, where I introduced an author index for the first time and added a new chapter (Chapter 15, Oxides). Volume 7 introduced Sections 378 (Oxides-Alkynes) through Section 390 (Oxides-Oxides). The Compendium is a handy desktop reference that will remain a valuable tool to the working Organic chemist, allowing a “quick check” of the literature. It also allows one to “browse” for new reactions and transformations that may be of interest. The body of Organic literature is very large and the Compendium is a focused and highly representative review of the literature and is offered in that context. Compendium of Organic Synthetic Methods, Volume 9 contains both functional group transformations and carbon-carbon bond forming reactions from the literature appearing in the years 1993, 1994 and 1995. The classification schemes used for volumes 6-8 have been continued. Difunctional compounds appear in Chapter 16. The experienced user of the Compendium will require no special insructions for the use of Volume 9. Author citations and the Author Index have been continued as in Volumes 6-8. Every effort has been made to keep the manuscript error free. Where there are errors I take full responsibility. If there are questions or comments, the reader is encouraged to contact me directly at the address, phone, fax, or Email addresses given below. As I have througout my writing career, I thank my wife Sarah and my son Steven who have shown unfailing patience and devotion during this work. I also thank Darla Henderson, the editor of this volume. Michael

B. Smith

Department of Chemistry University of Connecticut 55 N. Eagleville Road Storrs, Connecticut 06269-3060 Voice phone: (860)-486-2881 Fax: (860)-486-2981 Email: smith @Inucleus.chem.unconn.edu

vii

ABBREVIATIONS 0 AC

Acetyl

acac AIBN aq*

Acetylacetonate azo-bis-isobutyronitrile Aqueous

&

/

CH3

9-Borabicyclo[3.3.1]nonylboryl

B9

9-BBN BER BINAP Bn Bz

9-Borabicyclo[3.3.1]nonane Borohydride exchange resin 2R,3S-2,2’-bis-(diphenylphosphino)-1,lr-binapthyl benzyl benzoyl

BOC

t-Butoxycarbonyl

0

&

Ot-Bu

Bu CAM CAN ccat.

2,2’-Bipyridyl n-Butyl Carboxamidomethyl Ceric ammonium nitrate cycloCatalytic

Cbz

Carbobenzyloxy

Chirald COD COT CP CSA CTAB

2S,3R-(+)-4-dimethylamino1,2-diphenyl-3-methylbutan-2-01 1$Cyclooctadienyl 1,3,5cyclooctatrienyl Cyclopentadienyl Camphorsulfonic acid Cl&I33NMe3+Brcetyltrimethylammonium bromide

bPY WPY)

CY (+jH OC DABCO dba DBE DBN DBU DCC

11)

Cyclohexyl Temperature in Degrees Centigrade 1,4-Diazobicyclo[2.2.2]octane dibenzylidene acetone 1,2-Dibromoethane 1,8-Diazabicyclo[5.4.0]undec-7-ene 1,5-Diazabicyclo[4,3,O]non-5-ene 1,3-Dicyclohexylcarbodiimide

-CH2CH2CH2CH3 (NH)2Ce(NO3)6 0 &

OCH2Ph

+o

BrCH2CH2Br

c-C6H13-N=C=N-c-C6H13 ix

X

DCE

ABBREVIATIONS

% de DEA DEAD Dibal-H Diphos (dppe) Diphos-4 (dppb) DMAP DMA DME

1,2-Dichloroethane 2, 3-Dichloro-5,6-dicyano1,4-benzoquinone % Diasteromeric excess Diethylamine Diethylazodicarboxylate Diisobutylaluminum hydride 1,2-bis-(Diphenylphosphino)ethane 1,4-his-(Diphenylphosphino)butane 4-Dimethylaminopyridine Dimethylacetamide Dimethoxyethane

DMF

N,N’-Dimethylformamide

DDQ

C1CH2CH2Cl

HN(CH2CH3)2 Et02C-N=NC02Et (Me2CHCH2)2AlH Ph2PCH2CH2PPh2 Ph2P(CH2)4PPh2

MeOCH2CH20Me 0 H

dmp dpm dPPb dPPe dPPf dPPP dvb e% ee EE Et EDA EDTA FMN fod FP FVP h hv 1,5-HD HMPA HMPT iPr LICA (LIPCA) LDA LHMDS LTMP MABR MAD mCPBA Me MEM Mes

K N(CH3)2

bis-[ 1,

ABBREVIATIONS

MeOCH2CH3SO2-

MOM MS MS MTM NAD NADP Napth NBD NBS NCS NIS Ni(R) NMP Oxone

Methoxymethyl Methanesulfonyl Molecular Sieves (3Aor 483 Methylthiomethyl Nicotinamide adenine dinucleotide Sodium triphosphopyridine nucleotide Napthy CC1oH$ Norbornadiene N-Bromosuccinimide N-Chlorosuccinimide N-Iodosuccinimide Raney nickel N-Methyl-2-pyrrolidinone 2 KHS05.KHS04aK2S04

0P

Polymeric backbone

PCC PDC PEG

Pyridinium chlorochromate Pyridinium dichromate Polyethylene glycol

Ph

Phenyl

PhH PhMe Phth pit

Benzene Toluene Phthaloyl 2-Pyridinecarboxylate

Pip

Piperidine

PMP

4-methoxyphenyl

Pr

n-Propyl

-CH2CH2CH3

PY

Pyridine

N- / 3

quant. Red-Al sBu sBuLi Siamyl TADDOI TASF TBAF TBDMS TBHP (t-BuOOH) t-Bu TEBA TEMPO

Quantitative yield [(MeOCH2CH20)2AlH2]Na set-Butyl set-Butyllithium Diisoamyl a,a,a’,a’-tetraaryl-4,5-dimethoxy-1,3-dioxolane tris-(Diethylamino)sulfonium difluorotrimethyl Tetrabutylammonium fluoride t-Butyldimethylsilyl t-Butylhydroperoxide tert-B utyl Triethylbenzylammonium Tetramethylpiperdinyloxy free radical

J

CH3SCH2-

to/ H-N

3

CH3CH2CH(CH3) CH3CH2CH(Li)CH3 (CH3)2CHCH(CH3)silicate n-Bu4N+F t-BuMe2Si Me3COOH -C(CH3)3 Bn(CH3)3N+

ABBREVIATIONS

xii

TFA TFAA Tf (OTf) THF THP TMEDA TMG TMS TMP TPAP To1 Tr TRIS Ts(Tos)

Trifluoroacetic acid Trifluoroacetic anhydride Triflate Tetrahydrofuran Tetrahydropyran Tetramethylethylenediamine 1,1,3,3-Tetramethylguanidine Trimethylsilyl 2,2,6,6-Tetramethylpiperidine tetra-n-Propylammonium perruthenate Tolyl Trityl Triisopropylphenylsulfonyl Tosyl = p-Toluenesulfonyl

N),,)

Sonication

xc

Chiral auxiliary

CF3COOH (CF3CO)20 -S02CF3(-OS02CF3)

Me2NCH2CH2NMe2 -Si(CH3)3

4-c#&H3 -CPh3 4-Mec6&

INDEX,

MONOFUNCTIONAL

COMPOUNDS

Sections–heavy type Pages–light type Blanks in the table correspond to sections for which no additional examples were found in the literature

Sect. Carboxylic Alcohols, Aldehydes

acids phenols

AmideS AIIli~S

Ketones

PREPARATION

Pg.

30A 45A 60A 90A 105A 180A

9 f: 115 137 206

OF ‘l

7

FROM

Alkynes

Catboxylic derivatives Alcohols,

1 1

acid phenols

31 11

Aldehydes Alkyls, methylenes, aryls Amid=

17 5

18 6

19 6

32 11

33 12

34 13

47 48

48 48

49 49

Ethers, epxoides Halides,

63

64

65

60

60

61

76 loo

77 100

106 140

107 140

121 156 137 171

166 183

167 184

Nitriles Alkenes Miscellaneous

78 101

80 102

52 51

98 129

99 129

113 146

114 148

109 144

111 145

123 156

124 158

128 159 140 172

184 208 199 217

1% 212

197 216

198 217

211 227

212 227

213 227

171 191

172 192

186 209 200 219

201 220

ml 178 173 193

12 3

14 3

15 3

25 7

27 8

29 8

30 9

44 39

45 41

40 29

41 30

55 52 70 65

129 160

159 179 174 193

188 209

71 70

203 220

204 221

217 228

218 228

219 228

59 54

70 55

87888990 112 113

113

113

103 132

104 132

105 133

118 153

72 71

101

130

131

102 131

116 150

117 151

115 149 130 161

131 161

132 161

145 173

146 173

147 174

160 179 175 195

162 181 176 1%

119 154 134 162 149 175

163 182

177 198

179 202

222 232

135 169 150 175

180 204 1% 211

207 223 221 232

120 154

165 182

192 210

20s 221 220 232

43 39 58 53

loo

1% 209

202 220

42 30 57 53

85 111

142 172 157 177

170 191

69 65

97 120

108 142

la3 208

54 52

83 110

96 119

169 189

53 51

82 108

94 118

168 186

39 26

81 102

93 117

138 171

24 7

38 26

68 64

153 176

(RH) Ketones

50 50

61

sulfonates

Hydrides

36 25

58

Amines Esters

23 7

10 2

223 233

209 223

210 225

234 233

225 233

*.. XIII

INDEX, Sections-heavy

DIFUNCTIONAL

COMPOUNDS

type

Pages-light type

Blanks in the table correspond to sections for which no additional examples wem found in the literature

305 337

316 242

326 252

335 283

343 288

307 238

318 243

328 261

337 284

345 290

309 239

320 244

310 239

L

311 239 378

xiv

322 244

352 309

358 325

363 340

359

364

330 267

347 293

354 312

340 330

365 344

331 274

348 296

355 315

361 334

366 350

332 276

341 284

349 296

356

362

367

380

381

382

383

384

385

368

386

INTRODUCTION Relationship between Volume 9 and Previous Volumes. Compendium of Organic Synthetic Methods, Volume 9 presents about 1200 examples of published reactions for the preparation of monofunctional compounds, updating the 10650 in Volumes l-8. Volume 9 contains about 800 examples of reactions which prepare of difunctional compounds with various functional groups. Reviews have long been a feature of this series and Volume 9 adds almost 90 pertinent reviews in the various sections. Volume 9 contains approximately 1000 fewer entries than Volume 8 for an identical three-year period, primarily for difunctional compunds. Interestingly, there are about 500 fewer citations from the most cited journal (Tetrahedron Letters) than in the previous edition. Whether this represents a trend in the literature or an inadvertent selectivity on my part is unknown, but there has been a clear increase in biochemical and total synthesis papers which may account for this. Chapters l-l 4 continue as in Volumes l-8, as does Chapter 15, introduced in Volume 6. Difunctional compounds appear in Chapter 16, as in Volumes 6 and 7. The sections on oxides as part of difunctional compounds, introduced in Volume 7, continues in Chapter 16 of Volumes 8 and 9 with Sections 378 (Oxides-Alkynes) through Section 390 (Oxides-Oxides). Following Chapter 16 is a complete alphabetical listing of all authors (last name, initials). The authors for each citation appear below the reaction. The principle author is indicated by underlining (i.e., Kwon, T.W.; Smith, M. B.), as in Volumes 7 and 8. Classification and Organization of Reactions Forming Monofunctional Compounds. Chemical transformations are classified according to the reacting functional group of the starting material and the functional group formed. Those reactions that give products with the same functional group form a chapter. The reactions in each chapter are further classified into sections on the basis of the functional group of the starting material. Within each section, reactions are loosely arranged in ascending order of year cited (1993-1995), although an effort has been made to put similar reactions together when possible. Review articles are collected at the end of each appropriate section. The classification is unaffected by allylic, vinylic, or acetylenic unsaturation appearing in both starting material and product, or by increases or decreases in the length of carbon chains; for example, the reactions t-BuOH PhCOOH, and PhCH=CHCH20H t-BuCOOH, PhCH20H PhCH=CHCOOH would all be considered as preparations of carboxylic acids from alcohols. Conjugate reduction and alkylation of unsaturated xv

xvi

INTRODUCTION

ketones, aldehydes, esters, acids, and nitriles have been placed in Sections 740 and 74E (Alkyls from Alkenes), respectively. The terms hydrides, alkyls, and aryls classify compounds containing reacting hydrogens, alkyl groups, and aryl groups, respectively; for example, RCH2-H – RCH2COOH (carboxylic acids from hydrides), RMe – RCOOH (carboxylic acids from alkyls), RPh – RCOOH (carboxylic acids from aryls). Note the distinction between R2CO – R2CH2 (methylenes from ketones) and RCOR’ – RH (hydrides from ketones). Alkylations involving additions across double bonds are found in Section 74 (alkyls, methylenes, and aryls from alkenes). The following examples illustrate the classfication of some potentially confusing cases: RCH=CHCOOH RCH=CH2 ArH ArH RCHO RCH=CHCHO RCHO R2CH2 RCH2COR RCH=CH2

– RCH=CH2 – RCH=CHCOOH – ArCOOH – ArOAc – RH – RCH=CH2 – RCH3 – R2C0 – R2CHCOR – RCH2CH3

RBr + HC-CH

RCH-CR

ROH + RCOOH

RCOOR

RCH=CHCHO

RCH2CH2CH0

RCH=CHCN

RCH2CH2CN

Hydrides from carboxylic acids Carboxylic acids from hydrides Carboxylic acids from hydrides Esters from hydrides Hydrides from aldehydes Hydrides from aldehydes Alkyls from aldehydes Ketones from methylenes Ketones from ketones Alkyls from alkenes (Hydrogenation of Alkenes) Alkynes from halides; also al kynes from al kynes Esters from alcohols; also esters from carboxylic acids Alkyls from alkenes (Conjugate Reduction) Alkyls from alkenes (Conjugate Rduction)

How to Use the Book to Locate Examples of the Preparation of Protection Examples of the preparation of one funcof Monofunctional Compounds. tional group from another are found in the monofunctional index on p. x, which lists the corresponding section and page. Sections that contain examples of the reactions of a functional group are found in the horizontal rows of this index. Section 1 gives examples of the reactions of alkynes that form new alkynes; Section 16 gives reactions of alkynes that form carboxylic acids; and Section 31 gives reactions of alkynes that form alcohols. Examples of alkylation, dealkylation, homologation, isomerization, and transposition are found in Sections 1, 17, 33, and so on, lying close to a diagonal of the index. These sections correspond to such topics as the preparation of alkynes from alkynes; carboxylic acids from carboxylic acids; and

INTRODUCTION

xvii

alcohols, thiols, and phenols from alcohols, thiols, and phenols. Alkylations that involve conjugate additions across a double bond are found in Section 74E (Alkyls, Methylenes, and Aryls from Alkenes). Examples of name reactions can be found by first considering the nature of the starting material and product. The Wittig reaction, for instance, is in Section 199 (Alkenes from Aldehydes) and Section 207 (Alkenes frorm Ketones). The aldol condensation can be found in the chapters on difunctional compounds in Section 324 (Alcohol, Thiol-Aldehyde) and in Section 330 (Alcohol, Thiol-Ketone). Examples of the protection of alkynes, carboxylic acids, alcohols, phenols, aldehydes, amides, amines, esters, ketones, and alkenes are also indexed on p. xvii. Section (designated with an A: 15A, 30A, etc.) with “protecting group: reactions are located at the end of pertinent chapters. Some pairs of functional groups such as alcohol, ester; carboxylic acid, ester; amine, amide; and carboxylic acid, amide can be interconverted by simple reactions. When a member of these groups is the desired product or starting material, the other member should also be consulted in the text. The original literature must be used to determine the generality of reactions, although this is occasionally stated in the citation. This is only done in cases where such generality is stated clearly in the original citation. A reaction given in this book for a primary aliphatic substrate may also be applicable to tertiary or aromatic compounds. This book provides very limited experimental conditions or precautions and the reader is referred to the original literature before attempting a reaction. In no instance should a citation in

this book be taken as a complete experimental procedure. Failure to refer to the original literature prior to beginning laboratory work could be hazardous. The original papers usually yield a further set of references to previous work. Papers that appear after those publications can usually be found by consulting Chemical Abstracts and the Science Citation Index.

Classification Compounds.

and Organization

of Reactions

Forming

Difunctional

This chapter considers all possible difunctional compounds formed from the groups acetylene, carboxylic acid, alcohol, thiol, aldehyde, amide, amine, ester, ether, epoxide, thioether, halide, ketone, nitrile, and alkene. Reactions that form difunctional compounds are classified into sections on the basis of two functional grups in the product that are pertinent to the reaction. The relative positions of the groups do not affect the classification. Thus preparations of 1,2=amino=alcohols, 1,3-amino-alcohols, and 1,4amino-alcohols are included in a single section (Section 326, AlcoholAmine). Difunctional compounds that have an oxide as the second group are found in the appropriate section (Sections 278-290). The nitroketone product of oxidation of a nitroalcohol is found in Section 386 (Ketone-Oxide). Conversion of an oxide to another functional grup is generally found in the “Miscellaneous” section of the sections concerning monofunctional com-

.. . XVIII

INTRODUCTION

pounds. Conversion of a nitroalkane to an amine, for example is found in Section 105 (Amines from Miscellaneous Compounds). The following examples illustrate applications of this classification system: Difunctionaf Product RGC-C-CR RCH(OH)COOH RCH=CHOMe RCHF2 RCH(Br)CHzF RCH(OAc)CH20H RCH(OH)COzMe RCH=CHCH2C02Me RCH=CHOAc RCH(OMe)CH2SO2CH$H2OH RS02CH2CH20H

Section Et/e Alkyne-Alkyne Carboxylic acid-Alcohol Ether-Alkene Halide-Halide Halide-Halide Alcohol-Ester Alcohol-Ester Ester-Alkene Ester-Alkene Alcohol-Ether Alcohol-Oxide

How to Use the Book to Locate Examples of the Preparation of Difunctional Compounds. The difunctional index on pWxi gives the section and page corresponding to each difunctional product. Thus Section 327 (Alcohol, ThiolEster) contains examples of the preparation of hydroxyesters; Section 323 (Alcohol, Thiol-Alcohol, Thiol) contains examples of the preparation of diols. Some preparations of alkene and acetylenic compounds from alkene and acetylenic starting materials can, in principle, be classified in either the monofunctional or difunctional sections; for example, the transformation RCH=CHBr – RCH=CHCOOH could be considered as preparing carcompounds) or boxylic acids from halides (Section 25, monofunctional preparing a carboxylic acid-alkene (Section 322, difunctional compounds). The choice usually depends on the focus of the particular paper where this reaction was found. In such cases both sections should be consulted. Reactions applicable to both aldehyde and ketone starting materials are in many cases illustrated by an example that uses only one of them. Likewise, many citations for reactions found in the Aldehyde-X sections, will include examples that could be placed in the Ketone-X section. Again the choice is dictated by the paper where the reaction was found. Many literature preparations of difunctional compounds are extensions of the methods applicable to monofunctional compounds. As an example, the reaction RCI – ROH might be used for the preparation of diols from an appropriate dichloro compund. Such methods are difficult to categorize and may be found in either the monofunctional or difunctional sections, depending on the focus of the original paper. The user should bear in mind that the pairs of functional groups alcohol, ester; carboxylic acids, ester; amine, amide; and carboxylic acid, amide can be interconverted by simple reactions. Compounds of the type

INTRODUCTION

xix

RCH(OAc)CH20Ac (ester-ester) would thus be of interest to anyone preparing the diol RCH(OH)CH20H (alcohol-alcohol). Sources of Literature Citations. I thought it would be useful for a reader of this Compendium to see the distribution of citations used to this book (i.e., which journals have the most new synthetic methodology). As seen in the accompanying graph, Tetrahedron Letters and Journal of Organic Chemistry account for roughly 60% of all the citations in Volume 9. This book was not edited to favor one journal, category or type of article over another. Undoubtedly, my own personal preferences are part of the selection but I believe that this compilation is an accurate represention of new synthetic methods that appear in the literature for this period. Therefore, I believe the accompanying graph reflects those journals where new synthetic methodology is located. I should point out that the category “18 other journals” includes: Accts. Chem. Res.; Acta Chem. Stand.; Angew. Chem. Int. Ed. Engl.; Bull. Chim. Sot. Be/g.; Bull. Chim. Sot. Fr.; Can. J. Chem.; Chem. Ber.; Gazz. Chim. Ital.; Heterocycles; J. Chem. Sot.; J. Het. Chem.; J. Indian Chem. Sot; Liebigs Ann. Chem.; Org. Prep. Proceed Int.; Reel. Tram. Chim., Pays-Bas; and Tetrahedron Asymmetry. In addition, nine more journals were examined but no references were recorded.

18 other journals

KS Perkin I

Tetrahedron

Bull Chem Sot Jpn

Synthesis

JACS

Synth Commun

JCS, Chem Comm

Chem Lett

SynLett

J. Org. Chem.

Tetr. Lett.

Citations

xx INTRODUCTION

Compendium of Organic Synthetic Methods

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

CHAPTER

1

PREPARATION

SECTION

OF ALKYNES

1: ALKYNES

FROM

ALKYNES

Me2CHCH21,

THF

——–SiMePhz

t ;SiMePh,

SmIzSm

80% Murakami.

M,; Hayashi, M.; Ito. YJynlett,

1994,

179 Ph

(CH2)40AC

Ph

Ph , toluene

5% MO(C0)6 , llO°C , 2o”c 4-chlorophenol

AcO(H2C)4

Kaneta, N.; Hikichi,

E

AcO(H2C)4

K.; Asaka, S.; Uemura, M.; Mori, M. Chem. L&t., 1995,

80% 1055

REVIEW: “Palladium And/Or Copper-Mediated Cross-Coupling Reactions Between 1-Alkynes And Vinyl, Aryl, 1-Alkynyl, 1,2Propadienyl, Propargyl And Allylic Halides Or Related Compounds. A Review,” Rossi. R,; Carpita, A.; Bellina, F. Org. Prep. Proceed. Znt., 1995, 27, 129

SECTION

2: ALKYNES

FROM

A4CID DERIVATIVES

NO ADDITIONAL

SECTION

3: ALKYNES

FROM

ALCOHOLS

NO ADDITIONAL

SECTION

4: ALKYNES

FROM

EXAMPLES

AND THIOLS

EXAMPLES

ALDEHYDES

NO ADDITIONAL

EXAMPLES

Compendium

SECTION

5:

of Organic Synthetic Methods, Vol9

ALKYNES FROM AND ARYLS

ALKYLS,

NO ADDITIONAL

SECTION

6:

ALKYNES

FROM

7:

ALKYNES

AMIDES

FROM

EXAMPLES

AMINES

NO ADDITIONAL

SECTION

8:

ALKYNES

FROM

EXAMPLES

ESTERS

NO ADDITIONAL

SECTION

9:

ALKYNES FROM THIOETHERS

EXAMPLES

ETHERS,

NO ADDITIONAL

SECTION

10:

ALKYNES

METHYLENES

EXAMPLES

NO ADDITIONAL

SECTION

FROM

EPOXIDES

HALIDES

AND SULFONATES

HO.++K2C03

N.D.P, Synlett, 1995,

AND

EXAMPLES

-NO2

Pd/C , PPh3, CuI , DME

Bleicher, L.; Cosfwd.

Section 10

98% 111 5

Bu

Lett., 1994, 35, 6993

Section 15

SECTION

Alkynes from Misc.

11:

ALKYNES

FROM

HYDRIDES

For examples of the reaction RC=CH + R&C-C=CR1, (Alkyne-Alkyne). NO ADDITIONAL

SECTION

12:

ALKYNES

FROM

0

2

Ph I

Taniguchi,

KETONES

Y.; Takai, K.; Fujiwara,

TMSC(Li)Nz,

THF

-78OC + reflux Me Miwa, K.; Aoyama. T.: Shioiri, T, Synlett, 1994,

13:

ALKYNES

FROM

14:

Ph

=

Ph

ALKYNES

FROM

67% Y. Chem. Lett., 199% 1165

*

P-Me

58%

107

NITRILES

NO ADDITIONAL

SECTION

*

-1OOC ,20 min

SiMe3

Y.; Fujii, N.; Makioka,

SECTION

EXAMPLF;

Yb,THF,HMPA

0

see section 300

EXAMPLES

ALKENES OSiPhzt-Bu

NaHMDS , THF -100°C Grandjean, D.; Pale, P.; Chuche, J. Tetrahedron

SECTION

15:

ALKYNES

FROM

V

98%

L&t., 1994, 35, 3529

MISCELLANEOUS

COMPOUNDS

FVP (750°C) w t-Bu

Aitken. From A&ken. 1994,

=t-Bu

82% R,A,; Atherton, J.I. J. Chem. Sot., Per-kin Trans. l., 1994, 128 1 arylC0 derivatives: R.A.; Horsburgh, C.E.R.; McCreadie, J.G.; Seth, S. J. Chem. Sot., Perkin Trans. l., 1727

4

SECTION

Compendium

15A:

of Organic Synthetic Methods, Vo19

PROTECTION

OF ALKYNES

NO ADDITIONAL

EXAMPLB

Section 15A

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

Section 17

Acids from Acids

CHAPTER

2

PREPARATION

SECTION

16:

SECTION

OF

ACID

ACID DERIVATIVES

ACID

17:

DERIVATIVES

FROM

NO ADDITIONAL

EXAMPLES

DERIVATIVES

FROM

ALKYNES

ACID

DERIVATIVES

C02H HO

HaG,, @b, A BuLi, THF-HMPA

A I

v

*

OTs

+

6

Jv

d

OMe Me0

Me0

.

Kusumoto.T.;

1) 82% (10 Ichikawa, S.; Asaka, K.; Sato, K.; Hiyama, T. Tekhedron Lett., 1995,

36,

0 C02H

KF , microwave,

4 min 0

OAc

C02H
95%ee]

Mikami. K,; Yajima, T.; Terada,M.; Uchimaru, T. Tetrahedron Mt., 1993, 34, 7591 mSnBu3

, MS4A, CH2C12 t 20% (binol)TiClz , rt , 2d

PhCHO

96% (82% ee , S) Costa, A.L.; Piazza, M.G.; Tanliavini, E,; Trombini, C.; 1[Jmani-Ronchi. A, J. Am. Chem. Sot., 1993, 115, 7001 1.

Ti(OiPr)dl,l’-bi-2-naphthol , MS4A CH2C12,reflux

PhCHO

-78OC,10 min 2. m

OH Phk

SnBu3 , -20°C, 70h

88% (95% ee, R) J(eck. G&; Tarbet, K.H.; Geraci, L.S. J. Am. Chem. Sot., 1993, I15, 8467 1. Et$Zn ,25OC, 10% Lie\\ PhCHO 2.2N HCl 80% ee Mehler, T.; Martens.;

Wallbaum, S. Synth. Commun., 1993, 23, 269 1

1. ZnEt2 , 10%

CP

PhCHO

N H

11”1CPh20H

OH

2.2N HCl , -2OOC 100%ee Wallbaum, S.; m. J, Tetrahedron Asymmetry, 1993, 4, 637 With a chiral oxazoline additive, 60% ee J.m Tetrahedron Asymmetry, 1993, 4, 649 Allen, J.V.; Frost, C.G.; W-s.

16

Compendiumof Organic Synthetic Methods, Vol9

Section34B

1. BuLi 2. PhCHO

h

CPhzOH

OH

N Me

3. znEt2

4.2N HCl

Behnen, W.; Mehler, T.; Martens. TI Tetrahedron Asymmetry, 1993,4, 1413

OH

Et2Zn , toluene , hexane

PhCHO

98% ee , S

A 95% (85% ee, R)

Et

de Vries, E.F.J.; mee. 1987

Fit

J,; Kruse, C.G.; van der Gen, A. Tetrahedron Asymmetry, 1993, 4, OH

ZnEt2,5% iPr2NH

PhCHO

y i

5%

*

PhL

Ph-

quant. (46% ee , R) ShengJian, L.; Yaozhonrr. J,; Aiqiao, M.; Guishu, Y. J. Chem. Sot., Perkin Trans. I., 1993, 885 Et2Zn . PhMe , rt PhCHO

90% (96% ee , R) ao.

Rx;

Kim, N. Tetrahedron Lett., 1994, 35, 4115 CHo I

Me2Zn , PhMe , O°C, NHTf

Ti(Ot-Bu)4,8% TTPWI

I

a

NHTf

with Ti(OiPr)d – 80% yield, 0% ee Nowotng, S.; Vettel, S.; Mel, P, Tetrahedron Lett., 1994, 35, 4539

17

Alcohols from Amides

Section 36

Bu$n PhCHO , (R)-Binol +

0.5 Ti(OiPr), , -2O”d /

..

(14

1) 48%

>99% ee Keck. G.E,; Krishnamurthy, D.; Chen, X. Tetrahedron Lett., 1994, 35, 8323 PhCHO

OH

ZnEtz , hexaneftoluene, 10% chiral ligand 20°C, 28h

72% (80% ee) Perez-Encabo,A. Tetrahedron Asymmetry, 1994, 5,

And&, KM.; Martinez, M.A.; Pedro-; 67

ZnEt;! ,5% chiral ligand PhCHO

16h 70% (68% ee , R)

Ishizaki, M.; Fujita, K.; Shimamoto,M.; -0.

0, Tetrahedron Asymmetry, 1994, 5, 411

H

Et$Zn

PhCHO

*

Me%4 * N 3

P h‘\c

Ph-L

SH

94% (100% ee)

Kanrz, J,; Lee, J.W.; Kim, J.I. J. Chem. Sot. Chem. Commun., 1994, 2009

CHO

P ’

0

Ph

Watanabe,M.; Soai.

OH

Et$n ,18h

0

Ph J. Chem. Sot., Perkin Trans. I., 1994, 3125

quant. (93% ee)

18

Compendiumof Organic Synthetic Methods, Vol9

Et$Zn ,22OC

H

PhCHO 10% Stingl, K.; w.

~111 CH (Mes)OLi

00

Section34B

) *

PhL 70-90% (86% ee , S)

N Bn

J, Liebigs Ann. Chem., 1994,49 1 Et$n , chiral ferrocenecatalyst

PhCHO

85% (55% ee , R)

toluene mawa.

S,; Tsudzuki, IS. Tetrahedron Asymmetry, 1995, 6, 1039

PhCHO CH2C12, -78OC

Phw 93% (79% ee)

I(obavashl.. S,; Nishio, K. Tetrahedron L&t., 1995, 36, 6729 Bu3Sn-

, CH2C12,MS * c7H15L 58% (87% ee) 20% Zr-BINOL derivative Bedeschi,P.; Casolari, S.; Costa,A.L.; Tagliavini, E,; Umani-Ronchi, A. Tetrahedron Lett., 1995, 36, 7897 C7H&HO

1. chiral Ti complex , ether Ph/

CHO *

2TFA,THF

pi0

OTMS 97% (80% ee) Singer, R.A.; &reira.

E.M, J. Am. Chem. Sot., 1995, 117, 12360

NON-ASYMMETRIC Sn(CH$H=CH& Ph-

ALKYLATIONS

, D-arabinose, rt

CHO 5% Sc(OTf), , aq. MeCN

Hachiya, I.; Kobayashi, S. J. Org. Chem., 1993, 58, 6958

*

PhL

98%

Section 36

Alcohols from Amides

/m

Ph

19

PhCHO , Et$n , THF cat. Pd(PPh& , rt ,3h

H I

0

PJJ

88% Yasui, K.; Goto, Y.; Yajima, T.; Taniseki, Y.; Fugami, K.; Tanaka, A.; Tamaru. Y, Tetrahedron Lett., 1993, 34, 7619 diethyl ether, -5OOC PhCHO

98% t-Bu-

Et

(99 syn;anti) Wissing, E.; Havennith, R.W.A.; Boersma, J.; Smeets, W.J.J.; Spek, A.L.; van Koten, G,J. Org. Chem., 1993, 58, 4228 BuCHO + t-BuCHgHO

t

Ph

Bu OH

PhTi(OiP& , -4OOC 2 MAPH , PhLi , -78OC

Ph

t-BuHg +

OH 1) 60% 10.8) 60%

.. ..

(3 3 (1’

MAPH = ArOAr, Ar = 2,5diphenylphenyl Maruoka, K.; Saito, S.; Conception, A.B.; Yamamoto. H, J. Am. Chem. Sot., 1993, 115, 1183 , THF/aq. HCl

C7H fi—CHO

20°C, lh

*

C7Hl5L

>99% Yanagisawa, A.; Inoue, H.; Morodome, M.; Yamamoto. H, J. Am. Chem. Sot., 1993, 115, 10356 e

SnBu3

, CH2C12, 25OC

PhCHO

83%

5% Ir(CO)(PPh&C104, 30h Nuss. J.M,; Rennels, R.A. Chem. Lett., 1993, 197 1. e

I

, SnC12.2 Hz0 *

PhCHO NaI,DMF

,hL

2,30%NH4F,H20 89% Imai, T,; Nishida, S. Synthesis, 1993, 395

20

Compendiumof Organic Synthetic Methods, Vo19

Section34B

1. Bu$nSiMe3, THF, rt 3h,[email protected]

PhBCHO

2. H30+

SnBu3

Bhatt, R.K.; Ye, J.; Falck. J.R. Tetrahedron Lett., 1994, 35, 4081

m

PhCHO

SnBu3

5% Yb(OTf)3 85% Aspinall, H.C.; Browning, A.F.; Beeves N,; Ravenscroft,P. Tetrahedron Lett., 1994, 35,4639 mBr

,DMF,rrt *

ph//CHo GeI2 , lh

Phi 85%

Hashimoto, Y.; Kagoshima, H.; -0.

K, Tetrahedron Lett., 1994, 35,4805

OTIPS TIPS0

Ih40#‘,,, OTIPS /

1 [email protected] &HO , Me2AlCl , hexane -78OC,17h

SMe chirality

transfer

ene reaction

Masaya, K.; Tanino, K.; Kuwajima. I, Tetrahedron Lett., 1994, 35, 7965

BuGn-noMe :.I::b’” *-780zpJOMe

OMe

90% (70:30 de) Colombo. L,; DiGiacomo, M.; Brusotti, G.; Delougu, G. Tetrahedron Lett., 1994, 35, 2063 H

1. Li (powder) , naphthalene PhS02Et 2. Li (powder) , naphthalene * 3. PhCHO Guijarro, D.; m.

b& Tetrahedron Lett., 1994, 35, 2965

E -(I

61% Ph

Section 36

Alcohols from Amides

21

*3

SiMQ

sink3

l.Ga,KI,LiCl PhCHO , TI-IF , reflux w 2. H30+ H 4 Br

+ H

,8‘

x

Ph

Ph ..

(91 Han, Y.; Huansz. Y.-Z, Tetrahedron Lett., 1994, 35,9433

C,H7-

SnBug

cd413cHo

9) 95%

+

H

HO

w7

BuSnC13, CHCl3 , O°C

..

(98 Mipki.

2) 86%

H,; Yamamura, K. Chem. Lett., 1994, 897 10.5 CuCl , THF ) It

1. mBr

t

PhCHO 1.5 SnClp2 Hz0 , Id 2.30% aq. NI-IP

PhL 98%

T.Y; Nishida, S. J. Chem. Sot. Chem. Commun., 1994, 273

m

Ph EtCHO , Zn , aq. NH&I, Ph-Cl

Et

OH 98% (73:27) Rairama, R.; Ahonen, M. J. Chem. Sot. Chem. Commun., 1994, 1217

WR.; l

THF *

. .

cat. Pd(PPh& , PhCHO wso2ph

Et+,

THF , reflux

Ph 86%

Clayden, J.; lulia.M,

J. Chem. Sot. Chem. Commun., 1994, 1905

22

Compendiumof Organic Synthetic Methods, Vol9

mso2ph

l*

Section 34B

pd(pph3)4

2.2 Et2Zn , CgHlgCHO THF , reflux Clayden. JJ Julia, M. J. Chem. Sot. Chem. Commun., 1994,226l Ph PhCHzSiMe3, hv , MeCN

OSiMe3

Mg(C104)2, 6.5h

Fukuzumi. S,; Okamoto, T.; Otera. J, J. Am. Chem. Sot., 1994, 116, 5503 Cl 2: PhCHO ,THF , -78OC ’ Ba* c7Hyph+ C7H15

HO47Hfi

d

Ph ..

3) 80% (>99:1 E.-z) Yanagisawa, A.; Habaue, S.; Yasue, K.; mamoto. K J. Am. Chem. Sot., 1994, 116, 6130

(97

CHO

QH = MSnBu3

> InC13, acetone, Sh , -78OC+ rt (98:2 anti:syn)

Mar&B.

J.k; Hinkle, K.W. J. Org. Chem., 1995, 60, 1920 1. PhCHO , DMF , O°C

mSiQ3

2. H20 Kobavashi. S,; Nishio, K. J. Org. Chem., 1995, 60, 6620

Ph

Section 36

Alcohols from Amides

[email protected]$rCpCi ,20% ZnBr2 * THF ,3h, 25OC

PhCHO Zheng, B.; Bebnik.

23

Hz0

88%

J. Org. Chem., 1995, 60, 3278 In, H20,30 min

PhCHO

Br&

::OH Ph

Br

75%

I& C-J, Tetrahedron Lett., 1995, 36, 517

Me 1. Ti(OiPr)4 , iPrMgC1

4

+

OH

HO

i Ph . 84) 81% (16 Harada,K.; Urabe, H.; Sate. FcTetrahedron Lett., 1995, 36, i203 Nakagawa,T.; Kasatkin, A.; Sate. F, Tetrahedron Lett., 1995, 36, 3207

~cHooo

1. TMSOTf, CH& MqS , -78°C

2. Bu$nCH2CH=CH2 -40°C 3. TBAF

d3 (>99

m.

:

OH

’ 91% MPMO Kanq. S.-K,; Park, D.-C.; Park, C.-H.; Jang, S.-B. Synth. Commun., 1995, 25, 1359

Alcohols from Amides

Section 36

BrN

PhCHO

25

, Sn , Me$iCl 89%

Bu&Br , MeOH, rt ,4h Zhou, J.-Y.; Yao, X.-B.; Chen, Z.-G.; Wu. S.-H,Synth. Commun., 1995, 25, 3081

PhCHO

aSnBu3 ,THF,lt,4d * PhL

90%

pta2(pph3)2

Nakamura, H.; Asao, N.; mote.

w

Y, .I. Chem. Sot. Chem. Commun., 1995, 1273

13CHO

CH2C12-H20 (9.1 .. . H20, Bu$JBr (1 asuama. Y,; Kishida, M.; Kurusu, Y. J. Chem. Sot. Chem. Cohun.,

9) 48% 99) 48%

1995, 1405

REVIEW: “Synthetic Organoindium Chemistry: What Makes Indium So Appealing,” Cintas. P, Synlett, 1995, 1087

ALCOHOLS AND THIOLS FROM ALKYLS, METHYLENES AND ARYLS

SECTION 35:

No examplesof the reaction RR1 + ROH (R1 = alkyl, aryl, etc.) occur in the literature. For reactionsof the type RH + ROH (R = alkyl or aryl) seeSection 41 (Alcohols and Phenolsfrom Hydrides). NO ADDITIONAL EXAMPLES

SECTION 36: ALCOHOLS AND THIOLS FROM AMIDES 0 C6h3

LiBH3P-Pyr , THF, 25OC LA

*

N Pyr = pyrrolidino 3

Fisher, G.B.; Fuller, J.C.; Harrison, J.; Goralski, C.T.; Sinearam. B, Tetrahedron Lett., 1993, 34, 1091

(-13/OH

71%

26

Compendiumof Organic Synthetic Methods, Vol9

Section 39

SECTION 37: ALCOHOLS AND THIOLS FROM AMINES NO ADDITIONAL EXAMPLES

SECTION 38: ALCOHOLS AND THIOLS FROM ESTERS Pi,

180°C, 15h

e H+Bu 68% OBu Vega, F.R.; Clement, J.-C.; des Abbayes,H. Tetrahedron Lett., 1993, 34, 8117 Mg , MeOH, rt ,2.5h Me0 Y.-C,; Lebeau,E.; Walker, C. Tetrahedron Lett., 1994, 35, 6207

98%

1. PMHS , Ti(OiPr)J , THF Ph-C&Me

t

2. NaOH

PhCH20H

86$

PMHS = polymethylhydrosiloxane Breedon, S.W.; bwrence. N.J, Synlett, 1994, 833 1.2.5 eq. PHMS ,25% Ti(OiPr)d 65OC, Id CgHlg-COzEt t 2. aq. NaOH , THF Reding, M.T.; Buchwald. S.L,J. Org. Chem., 1995, 60, 7884 C7HfiCH2SAc

OH C9H19

93%

BER , Pd(OAc)z , MeOH, reflux w C7HfiCH2SI-I

BER = borohydride exchangeresin Choi, J.; Yoon. N.M,Synth. Commun., 1995, 25, 2655

SECTION 39:

/

98%

ALCOHOLS AND THIOLS FROM ETHERS, EPOXIDES AND THIOETHERS Bu,CuCNLi2,

THF OH

products are converted to alkenes via Swem oxidation and elimination

(95

Chauret, DC.; Bong, J.hl, Tetrahedron Lett., 1993, 34, 3695

+ :

Bu 5) 8040%

Section 39

Alcohols from Ethers

27

OH

OH

YJ

v

Al(Hg) , 10% aq. NaHC03

yield is 23% without ultrasound

also used Zn rather than Al(Hg)

ando Moreno. M.J.S SacMelo, M.L.; CamposNeves, A.S. hedron Lett., 1993:‘34, 353 Salvador, J.A.R.; S&eMelo. M.L,; CamposNeves, A.S. Tetrahedron Mt., 1993, 34, 361 l

Phi , Pd(PPh&$

, Zn , ZnCl2

Ph

THF,60°C,4h,NEt3 Duan, J.-P.; Chew. C-H, Tetrahedron Lett., 1993, 34,4019 1. LiI , MeCN , Amberlyst 15 rt, 30min MOTS

***+o = 3

= = &H

2. Bu$nH , AIBN , 80°C toluene ,2h

MOT,

Federici, C.; &i&i. G,; Rossi, L.; B Lett., 1994, 35, 797

99~88%

C,; Chiummiento, L.; Funicello, M. Tetrahedron

H2, Pd-C ,16h

t

P-OH HO

86%

Me

Bach, T, Tetrahedron Lett., 1994, 35, 1855

l aI

OH ’ 10% Pd(OAc)z

5 eq. NaO$H ,2 eq. BufiCl 3 eq. iPr2NEt , 80°C, Id N,N-dimethylacetamide Larock. RC,; Ding, S. J. Org. Chem., 1993, 58, 804

I (69:31 E.2)

70%

28

Compendiumof Organic Synthetic Methods, Vol9

zH *aa

Section 39

Mg , MeOH

,,,[email protected] / BnO

7-L

C02Me

H

98%

p;als. CA; Lee, E.; Lee, G.H. J. Org. Chem., 1993, 58, 1523

Pd/C , HCO2NH4, EtOH

0 w-h7

OH /

Al

23OC, 2d

W-h

Dragovich. P.S,; Prins, T.J.; Zhou, R. J. Org. Chem., 1995, 60, 4922

A

81%

98% Beugelmans, R.; Bourdet, S.; Bigot, A.; Zhu. L Tetrahedron Lett., I994, 35, 4349

)

Te9LiBT3,n

)

I

TsO Kumar, A.; m.

4

D.C: Tetrahedron Let?., 1994, 35, 5583 L-Selectride , THF ,67OC, 12h

Wheless, K. Tetrahedron Let?., 1994, 35, 8727

1. TMSN3 , W(Nt-Bu)2(NHIt-Bu)2 ,5d w

Ph

2. H+

OH

95%

[ with Cr(Nt-Bu)2C12;12h – 95% ] Leunn. W.-H; Chow, E.K.F.; Wu, M.-C.; Kum, P.W.Y.; Yeunrr. L.-L, Tetrahedron Let?., 1995, 36, 107

29

Alcohols Tom Halides

Section 40

Ph

5% SmI2(THF)z, CH2C12

NEt2

Et2NH,rt,18h

(100

OH

+

..

0)

63%

regioselectivity of addition reversedwith Me&N3 to form azide-OTMS Van de Weghe, P.; collin. Tetrahedron Lett., 1995, 36, 1649

0

TMSN3, Ph&bOH, PhH reflux ,2h

67% 19% .. Funwara. M.; Tanaka,M.; Baba, A.; Ando, H.; Souma,Y. Tetrahedron Lett., 1995, 36, 4849 l.e-,Ni(II),Mganode,DMF,rt mOPh

*

PhOH

2. Hz0 99%

Olivero, S.; Dufiach. E, J. Chem. Sot. Chem. Commun., 1995,2497 Additional examplesof ethercleavagesmay be found in Section45A (Protection of Alcohols and Thiols).

SECTION 40:

ALCOHOLS AND THIOLS FROM HALIDES AND SULFONATES

02N-(-)-Br :::v::02N-(-)

a

Bieniarz. C,; Cornwall, M.J. Tetrahedron Lett., 1993, 34, 939

I

a.

.

/

Br

siMe3

1. Li dispersion, ether reflux 2. PhCHO , -1OOC lh

also works with ketones M; Hatano,K.; Kimura, M.; Watanabe,T.; Oriyama, T.; Koga, G. Tetrahedron Lett.,

1994, 35, 579

30

Compendiumof Organic Synthetic Methods, Vol9

Section42

1. Me3ZnLi , THF , -78OC

Ph-I

2. Me3Al, CHg12, O°C, lh

Ph 55%

Kondo, Y.; Takazawa,N.; Yamazaki, C.; Sakamoto.,J. org. chem., 1994, 59,4717

PhCHO –

PhCHCl2 2. NaB0~4 [email protected] ,2h

m

H

1. Bug , t-BuLi , -78OC

PC15

PhJL

G.W.; Lin, N.-S.; Yu, S. Tetrahedron Let?., 1995, 36;8545

Bu 64%

NHBn

NHBn

0 Yang, R.-Y.; Dai. I..-& Synth. Commun., 1994, 24, 2229

G Br

1. HC02NHEt3

CO2H 2.H20

80% J,; Renyer, M.L.; Veerapanane,H. Synth. Commun., 1995, 25, 3875

Mer.

SECTION 41: ALCOHOLS AND THIOLS FROM HYDRIDES

0 /

1. e- , CF$02H, CH2C12,NEt3

*

2.H20

(t /

Fujimoto, K.; Maekawa, H.; Tokuda, Y.; Matsubara,Y.; Mizuno, T.; Nishiguchi.

OH 73% SYnlett,

1995,661

SECTION 42: ALCOHOLS AND THIOLS FROM KETONES The following reaction typesare included in this section: A. Reductionsof Ketonesto Alcohols B. Alkylations of Ketones,forming Alcohols Coupling of ketonesto give diols is found in Section 323 (Alcohol + Alcohol).

Section42A

Reductionof Ketones

31

SECTION 42A: REDUCTION OF KETONES TO ALCOHOLS ASYMMETRIC

REDUCTION OH = Z I

BH3, THF , 80°C w

> 90% (92% e-e,R)

P ii

Quallich. GJ,; Woodall, T.M. Tetrahedron Lett., 1993, 34,4145

Me

85% (76%ee,R)

2.1N HC1 P Me Balm. (3,; Elder, M. Tetrahedron Lett., 1993, 34, 6041 G. candidium

CQzEt N

C02Et cyclopentanol H20, 70h

(7193syn:anti)

Me QH E _=

immobilized G. candidium hexane ,3h cyclopentanol

-/I/

(955 syn:anti)

G. candidium = Geotrichum candidum

Nakmura. KJ Takano, S.; Ohno, A. Tetrahedron Lett., 1993, 34, 6087 0.6 BHpSMe2 , THF rt,clh Me

M

10%

PA

R

H *

Y H

OH = =

+

Phl

P&Me

Me

P ’ ‘Ph

82% (27%ee,S)

Bums, B.;,Studley, J.R.; Wills. M, Tetrahedron Lett., 1993, 34, 7105

1.ld4j~; P

P

Me$iCl Me

2.2N HCl

H *

C02Et = = = = I

PhL

Me

92% (84% ee, R)

&-&IL C,; Seger,A.; Felder, M. Tetrahedron Lett., 1993, 34, 8079

32

Compendium of Organic Synthetic Methods, Vo19

Section 42A

2. SmI3, THF , ICHgH21 3. quench quant. (97% ee , R) Evans. D.pL; Nelson, S.G.; Gag&, M.R.; Muci, A.R. J. Am. Chem. Sue., 1993, 115, 9800 OH

1. P-TADDOL complex , Ph2SiH2 , PhH

50% (29.5:70.5 R.-S)

r~mw112 2. TsOH , MeOH

-APh

TADDOL = a,a,a’,&tetraaryl-4,5-dimethoxy-1,3-dioxolane Jakaki, J.-i.; Schweizer, W.B.; Seebach. D, Helv. Chim. Acta, 1993, 76, 2654 Bakers yeast (cell free extract) OAc

Ishihara, K.; Sakai, T.; Tsuboi, S.; IJtaka, 0

OAc

NaDPH ,8h

62% (>99% ee, S) Tetrahedron Let?., 1994, 35,4569

[ (COD)Rh(DiPFc) 1’ OTf H

Ph A

60 psi H2 ,25OC ,4h

L Ph

OH

DiPFc = 1, l’-bis-(diisopropylphosphino)ferrocene quant. Burk. MJ,; Harper, T.G.P.; Lee, J.R.; KaIberg, C. Tetrahedron Let?., 1994, 35, 4963

dcl

[email protected];;

dcy%@l.7%e,sJ

Hong, Y.; &D. Y.; Nie, X.; Zepp, C.M. Tetrahedron Let?., 1994, 35, 6631 Ph

1. Ph$iH2 ,5% Rh-diferrocenylTHF , o”c dichalcoginide

Ph *

67% (50% ee , R) 2.0.5M HCI/MeOH 0 OH Nishibayashi, Y.; Singh, J.D.; Segawa, IS.; Kukuzawa, S.i.; Uemura, S, J. Chem. Sot. Chem. Commun., 1994,1375

Section 42A

Reduction of Ketones

Bakers yeast sugar

OH

SH

C02Et

+

CO2Et

C02Et

.. (77 55% ee Tetrahedron Asymmetry, 1994, 5, 403

Nielsen, J.K.; Madsen.

Me

33

/L

23

immobilized Geotrichum candidurn

i)H = =

w hexane 2-hexanol

Ph

MeA

Ph

73% (>99% ee , S) Nakamura. K,; Inoue, Y.; Ohno, A. Tetrahedron Lett., 1995, 36, 265 OH

0

OH Ph

OH

(-)-B -chlorodiisopinocampheylborane -15OC + OOC, THF, pyridine

Ph

99% (96.4% ee) . Shteh. W.-C,; Cantrell Jr., W.R.; Carlson, J.A. Tetrahedron Lett., 1995, 36, 3797 Hz, (S-BINAP)zRuBrz COzMe

* MeOH, rt ,48h

OH == =

C02Me

80% (97% ee)

Genet.; Ratovelomanana-Vidal, V.; Ctio de Andrade, M.C.; Pfister, X.; Guerreiro, P.; Lenoir, J.Y. Tetrahedron Lett., 1995, 36, 4801

iL

H2 , iPrOH , chiral bis-phosphine

H

>99% (87% ee, R) * PhL chiral bis-amine Ph Ohkuma, T.; Ooka, H.; Hashiguchi, S.; Ikariya, T.; Novori. R,, J. Am. Chem. Sot., 1995, 117, 2675

4

Ph

[RuC12(mesitylene)]2, KOH , 15h TolO$HN+

/-f

Ph

N

NH2

Ph

Hashiguchi, S .; Fujii, A.; Takehara, J.; Ikariya, T.; &yori. 7562

OH PhA 95% (97% ee, S) & J. Am. Chem. Sot., 1995, I1 7,

34

Section 42A

Compendium of Organic Synthetic Methods, VoI 9

1. Ph2SiH2 , THF , 1% RhCl(NBD)zL chiral ferrocenyl phosphine ligand

0

OH 90% (87% ee , S)

PhA 2. H30+ * PhA . Havashl. T,; Hayashi, C.; Uozumi, Y. Tetrahedron Asymmetry, 1995,6, 2503 1.0.1 chiraI diol , hexane , -3OC , catecholborane 2. H30+ quant. (82% ee) Giffels, G.; Dreisbach, C.; Kragl, U.; Weigerding, M.; WaIdmann, H.; Wa~&ey. C1,Angew. Chem. Int. Ed. Engl., 1995, 34, 2005

NaBH4, EtOH Co (P-oxoaldiminato) complex

99% (73% ee , S) Nagata, T.; Yorozu, K.; Yamada, T.; Mukaiyama. T,Angew. Chem. Int. Ed. En& 1995, 34, 2145

NON-ASYMMETRIC

o= 0

REDUCTION

1. CdCl$Mg (powder) THF,15min

OH

92%

2, H20

Bordoloi. M, Tetrahedron Lett., 1993, 34, 1681

t-Bb

. olrm

(-)

o

LiAIH(zt2cMe3)3

~

t-Bu

with LiAlH(OCMe3)3 – 90: 10 trans:cis Cr.; Deberly, A.; Toneva, R. Synlett, 1993, 585

(-)

OH

5:95 trans:cis

Cu(I1) exchanged cationic resin ‘.,u-(-=’

NaBH4, EtOH, O°C

*

t-Bu-(-)-oH 98%

Sarkar. A,; Rao, B.R.; Ram, B. Synth. Commun., 1993, 23, 291

35

Reduction of Ketones

Section 42A

& :;:I;;

&

Fuller, J.C.; Staangeland, E.L.; Goralski, C.T.; Sinearam.

o=

Tetrahedron Lett., 1993, 34, 257

iPrOH , SiO2-Zr catalyst

0

Inada.;

92%

OH

reflux

87%

Shibagaki, M.; Nakanishi, Y.; Matsushita, H. Chem. Lett., 1993, 1795

0

OMe TiC14, MeflBH4 t

Ph

CH2C12 , -78°C

Ki other reducing agents also used Sarko, CR.; Guch, I.C.; Dime.

t-Bu

do

(99 M, J. Org. Chem., 1994, 59, 705

Liz;;;;H7)2

t ,:

1)

:

93%

&OH

99% Harrison, J.; Fuller, J.C.; Goralski, CT.; Singaram. B, Tetrahedron Lett., 1994, 35, 5201 OH

0 1. Cp2TiC12/NaBHq, 5 min 2.1 N NaOH % Barden, M.C.; Schwartz. J, J. Org. Chem., 1995, 60, 5963

B 0

(MeO)3SiH , LiOMe , ether

Ph

-20°C, 9h

*HOlph (8

+

XPh .

92) quant.

wth (Me0)$iI-I/HMPA/LiOMe/O°C/2h + (9O:lO) 98% Hojo, M.; Fujii, A.; Murakami, C.; Aihara, H.; Hosomi. Tetrahedron Lett., 1995, 36, 571

36

Compendium of Organic Synthetic Methods, Vol9

Section 42B

Hz (8 atm) , cat. RuClz(Binap)(dmf), -H

iPrOH , diamine , KOH ,28OC

d Ph Ph Ohkuma, T.; Ooka, H.; Ikariya, T.; Noyori. R,J. Am. Chem. Sot., 1995, 117, 10417

cat. [NiClz(PPh&

0

, cat. NaOH

OH 82%

– PhA iPrOH , Ar ,3Oh, heat PhA lyer. &; Varghese, J.P. J. Chem. Sot. Chem. Commun., 1995, 465

SECTION 42B: ALKYLATION

OF KETONES, FORMING ALCOHOLS

Aldol reactions are listed in Section 330 (Ketone-Alcohol)

o=

Me

/

0

Hebri, H.; Duiiach.;

e’ , SmC13, DMF , 20°C

Perichon, J. Tetrahedron Lett., 1993, 34, 1475 3 eq. Me$=CH2 , THF 0 -1OOC -+ rt

91% Hamett, J.J.; Alcaraz, L.; Mioskowski, C.; Martel, J.P.; LeGall, T.; Shin, D.-S.; Falck. J.K Tetrahedron Lett., 1994, 35, 2009

C6H13

-0.

JL

e’7 CH3

DMF , -OH Bu#BF4

+

.,,,330H OH

89% T,; Morishima, Y.; Moriyoshi, N.; Ishifune, M. J. Org. Chem., 1994, 59, 273

Section42B

Alkylation of Ketones

37

1.2.2 eq. SmI2 , THF 2 eq. t-BuOH

t

2. H30+

53% (1:l) &lolander. G.A,; McKie, J.A. J. Org. Chem., 1994, 59, 3186 0.05 CeC13,lh , THF 0

1.1

:= -MgBr

93% rtrov. V,; Bratavanov, S.; Simova, S.; Kostova, K. Tetrahedron Lett., 1994, 35, 6713

mBr C02Et

, In 91Oh CO2Et

aq. MeOH

Br9 wlust o=

76%

Ii. C.-k, Lu, Y.-Q. Tetrahedron Lett., 1995, 36, 2721

0

THF , 1Sh

1.8 Et$Zn , Ti(OiPr)4 , hexane

PhCHO Hang.;

80%

usescommercialZn dust Majee, A.; Das, A.R. Tetrahedron Lett., 1995, 36,&B

Ranu.;

OH

-23°C , 0.1 chiral catalyst Guo, C. Tetrahedron Lett., 1995, 36, 4947

Ph

Me3Ti*MeLi , ether W-h

97% 99% ee, S

w

-5OOC

Et

* W-h

selective for conjugated ketones in the presence of non-conjugated ketones M&& I&; Leung, C.W. J. Am. Chem. Sot., 1994, 116, 371

78%

Compendiumof Organic Synthetic Methods, Vol9

38

Section42B

1. 10%CpzTi(PMe3)2,Ph#I-I2 1111111111

*

OH

6 >60%

Kablaoui, N.M.; Buchwald. S.L,J. Am. Chem. Sot., 1995, 117, 6785

e’ , MeCN , ZnBr2 Bu4N BF4

.

(95 Row

5) 85%

Y,; Derien, S.; DuWach,E.; Gebehenne,C.; Perkho;, J. Tetrahedron, 1993, 49, 7723

wBr *

+

Zn , aq. NH&l, THF

(54 Ahonen, M.; SiiSholm.

m’ PhL

..

46) 73%

Chem. Lett., 1995, 341

Ph

9PbCr(~eda) THF , -6OOC

Ph 77%

WiDf. P,; Lim, S. J. Chem. Sot. Chem. Commun., 1993, 1655

. 11.G,; Marcantoni, E.; Petrini, M. Angew. Chem. Int. Ed. En&

70% 1993, 32, 1061

39

Alcohols from Alkenes

Section44

SECTION 43: ALCOHOLS AND THIOLS FROM NITRILES 1. Li (excess), PhCHO , -3OOC + MeCN 5% 4,4’-his-t-Bu biphenyl 2. H20, HCl Guijarro, D.; Yus. M, Tetrahedron, 1994, 50, 3441

H 39%

Me-L

Ph

SECTION 44: ALCOHOLS AND THIOLS FROM ALKENES 1. Ti(BH& , 30 min CH2C12,-2OOC -2.10% K2CO3

c(,

+

aOH

1.2) 82% (1 Kumar, K.S.R.; Baskaran,S.; Chandrasekaran,S. Tetrahedron Lek., 1993, 34, 171 Me

Zn(BH& , DMF SiO2, rt ,30 min 30) 80%

(70 &nu. B.C,; Charkraborty, R.; Saha,M. Tetrahedron Lett., 1993, 34,‘4659

a

l.Mg*,THF,rt 2. ethylene oxide THF , -78OC 3. co2, oc + rt

OI-

0

a

OH 86% with Mg* = 8 Li, naphthalene,4 MgC12, THF, 3 Li H30+ at -78OC Sell, M.S.; Xiong, H.; We. R.D. Tetrahedron Lett., 1993, 34, 6007 6011 40°C 4. H30+ , 0°C + -9

o 69%

1.2 eq. Ph02BH, THF Nb catalyst, 25OC, Id 2. H202, NaOH Burgess.K,; Jaspars,M. Tetrahedron Lett., 1993, 34, 6813 also with CpzTiC14, see Burgess.K,; van der Donk, W.A. Tetrahedron L&t., 1993, 34,6817

40

Section 44

Compendiumof Organic Synthetic Methods, Vo19

By 99% ee) 115, 12569

1993,

Hz, rt , lh , MeOWH20 RuC13,

TOA

TOA = trioctylamine Fache, F.; Lehuede, S.; LeMaire. M, Tetrahedron Lett., Ph 0 Cho, I.S.; Lee, B.; m

1995,

36,

99% (ciskans = 1.5) 885

[ (t-Bu2PH)Pd(Pt-Bu)2]2, H2 ,02 THF/CH2C12,6h

Tetrahedron Lett., 1995, 36, 6009

aq. Ba(OH), , NiAl(Raney alloy) 54%

60°C, lh

Br Br Tsukinoki, T.; Kakinami, T.; Iida, Y.; Ueno, M.; Ueno, Y.; Mashimo, T.; Tsuzuki, H.; Tashiro, M. J. Chem.Sot. Chem. Commun., 1995, 209 H2, [ W2(~&t’BU)6(@)2

1

Barry, J.T.; Chisholm.M.H, .I. Chem. Sot. Chem. Comma,

1995,

no yield 1599

74

Section 74B

Compendium of Organic Synthetic Methods, Vo19

SECTION

74B: Formation

of Aryls

OMe / LiCl , CuBr , inhibitor Pd(PPh& , dioxane , reflux

OMe &.& J.M.; MartoreU,G. J. Org. Chetn.,1993, 58, 1963

Crrissom, J.W,; Calkins, T.L.; McMillen,

bMe

H.A. J. Org. Chem., 1993, 58, 65% 50 at.mCO, [email protected] PdCl2W’bh 9 mt3

PhooAc

PhH , 140°C, 3h Ishii, Y.; Gao, C.; Xu, W.-X.; Iwasaki,M.; Hidai. MJ.

C

*

OAc 69% Org. Chem., 1993, 58, 6818

HSiMe$-Bu , C) (50 atm) Ru~(CO)~~/PCY~, 140°C,20h

*

*:::: 45%

Chatani, N.; Fukumoto, Y.; Ida, T.; Murai.

S, J, Am. Chem. SM., 1993, 11.5, 11614

PhOH , PhMe ,180”C t

7h %

0

Danheiser, R.L,; Gould, A.E.; de la Pradilla, R.F.; Helgason, A.L. J. Org. Chem., 19%

5514

5%

Section 74B

75

Formation of Aryls

20% Ni(O)-PPh3 , HC=CH N—Ts THF,23OC, 12h 91% Sato, Y.; Nishimata, T.; Mori. M, .I. Org. Chem.,

1994,

59, 6133

1. PhNH2 2. Pd(OAc), , MeCN PhCHO B

;-;FHT3/

.

0

AQtZ

RamaRao.AV,; Reddy,K.L.; Reddy,M.M. Tetrahedron Lett.,

1994,

35,

5039

OH 1.5 I

y

~wipr)3

t

I

0.1SnC14, 0°C 1.5 (MeO)$iMe3

s 78% -Si(iPr)3

Angle. SR,; Boyce,J.P. Tetrahedron

Lett., 1994,

35, 6461

t-BuOOCOPh, Cu(OAc), CuBr , PhH , 80°C, 8.5h

56% Tavares,F.; Mevers. A.1, Tetrahedron Lett., 1994, 35, 6803 N-OH Bn

5% Pd/C, diethyleneglycol 188OC , diethyl ether, 45 min

Bn 89%

I Ar Ar = 4-methoxyphenyl Matsumoto.M.; Tomizuka,J.; Suzuki, M. Synth. Commun.,

1994,

24,

Al1441

76

Compendium

SECTION

74C: Alkylations

Section 74C

of Organic Synthetic Methods, Vol9

and Arylations

of Alkenes

2 BFjmOEt2 25OC

Maietich. G,; Zhang, Y.; Feltman, T.L. Tetrahedron L&t., 1993, 34,441 . Maretich. G,; Zhang, Y.; Feltman, T.L.; Duncan Jr., S. Tetrahedron Lett., 1993, 34, 445 Ar

/OH Ph Toluene , -45OC , 18h 2. LiEt3BH 3. MeOH 4. NaBH4

. Tomloka.;

Ar = 2,6-di-t-Bu-4-OMephenyl Shindo, M.; Koga, K. Tetrahedron

N

M

/

80%

(84% ee)

Lett., 1993, 34, 681

+3-l”l

H

DMF , BuflCl , ld 10% Pd(OAc)z ,3 iPr2NEt 66:34 E.-Z, 99% 5 HC02Na Ding, S. Tetrahedron Lett., 1993, 34, 979

%

0

Larock.;

w-4

1

Me

cat. Pd(OAc);? , [email protected] DMF ,45OC, overnight

C02Me Wll

OH OH &[email protected]

T, Tetrahedron

L&t., 1993,

34,

1133

NH2

75%

Section 74C

Alkylation of Alkenes

77

Me

1. Et&Cl

60% 2. BuZnCl , DMF * BuJ==i OH 5% C12Pd(PPh3)2 2 BuLi ,5h Ay, M.; Gulevich, Y.V.; Noda, Y. Tetrahedron Lett., 1993, 34, 1437 OH

. . Nenlshl,;

0

SnBu3

v

10h

Zhang, H-C.; Brakta, M.; DavesJr,. G.D, Tetrahedron

OTf

0

0

L&t., 1993, 34, 1571

, 30°C, 91h 58% 87%ee,R

Pd(R-BINAP)2, PhH ProtonSponge C)zawa.F,; Kobatake,T.; wi.

Pi0

x

T, Tetrahedron Lett., 1993, 34, 2505

Q-I 11I, AIBN , To1 52%

46h, 85OC

SnBu3 Kinnev. W.A, Tetrahedron Lett., 1993, 34, 2715 PhBr , To1,2% Pd(PPh& phm,, Bu$nmNI-12 R.J&; Geng,B.; &Iore;ill. J.JE J. Org. Chem., 1993, 58, 1443 w-h7

00

w-b3

1. Me2SCHC02Et

H

Bu$n

B(W

l312

2. H202, NaOAc

Dem. M.-Z,; Li, N.-S.; Huanrr.Y.-Z,J. Org. Chem., 1993, 58, 1949

60%

47%

Compendium of Organic Synthetic Methods, Vo19

Section 74C

0

Br J&;

OMe

Qabar, M.N. J. Org. Chem., 1993,

58, 4473

1. PdC12 , LiCl , THF o”c + 25OC ] 2. aq. NH4Cl

-PhINH2

0

2. PhHgCl , O2 60% Larock. R.C%; Ding, S. J. Org. Chem., 1993,

E:z)

58, 2081

PhOTf , Pd(PPh3)4, 85OC

(CH2)8co2Me

/9-BBN

/

(74:26

&PO4 , dioxane

ph-

58,

2201

(cH2)&02Me 87%

Oh-e, T.; &Graura. N.: Suzuki. A, J. Org. Chem., 1993, Ph

1.2 Et$n , 1.5% PdC12(dppf), THF 2. CuCN.2 LiCl 3.

Stadmiiller, Sot., 1993,

C02Et

H.; Lentz, R.; Tucker, C.E.; S tiidemann, T.; Diirner, W.; Knochel. 115, 7027

phi

3 eq. EtMgBr , Cp$rCl2 THF,rt,6h

Suzuki, N.; Kondakov,

D.Y.; Takahashi,

T, J. Am. Chem. Sot., 1993, 11.5, 8485

J. Am. Chem.

Section 74C

Alkylation of Alkenes

79

C02Et N2+BFd

4

C02Et

, EtOH

2% Pd(OAc)z , 60°C, lh

SenguPta.;

Bhattacharyya, OH

71%

S. J. Chem. Sot., Perkin Trans. l., 1993, 1943 OH

5 eq. MeMgBr 0.05 PdC12(PPh3)2

97% VW,;

Giesen, V.; Fuest, M. Liebigs Ann. Chem., 1993, 629

e, , DMF , Et&104 47% Ni(teta)(ClO& Ozaki. S,; Horiguchi,

I.; Matsushita, H.; Ohmori, H. Tetrahedron

Lett., 1994, 35, 725 iMe

LDA, TMS-Cl C3H

06

Et Wright. S.W, Tetrahedron

THF , -78OC

*

C3H

Et

93%

Lett., 1994, 35, 1841 Phi , Bu4NHS04,

aq. MeOH

02Me

02Me 5% [Pd(OAc)2/2 PPh3] Jeffery. T, Tetrahedron

A Ph

96%

Heck reaction in aqueous media Lett., 1994, 35, 3051

0

0

Phi , SmIz/THF , 15 min DMSO

0 Nazareno, M.A.; Rossi. R.A, Tetrahedron

Ph A/ Lett., 1994, 35, 5185

Ph

47%

Compendium

of Organic Synthetic Methods, Vol9

Section 74C

Ph Pd(OAc)2, Bu3P, 3h IS2CO3 , DMF , 80°C +

Phi

Ph +

quant. (78 Ono, IS.; Fugami, K.; Tanaka, S.; Tamaru. Y, Tetrahedron Lett., 1994, 0

I

Majetich.

OOCNHMe 6) 35, 4133

0 2 AlEt

, 0°C b

SPh

10h

G,; Zhang, Y.; Liu, S. Tetrahedron

SPh

I

0 Lett., 1994,

4 35,4887

0

70%

,SnBuj

Pd(PPh3)4, THF ,65OC, lh Matthews,

D.P.; Waid, P.P.; Sabol. J.S.: McCarthy. J.R, Tetrahedron

66% Lett., 1994, 35, 5177

TfO OMe

SnBu3

OMe 70%

B.

D,; Cardamone, Rbe9 Guzzi, U. Tetrahedron l

/ SnBu3 1. 5% Pd2(dba)3 ,20% AsPh3 w 2.5% TFA , CH2C12 = Rink amide resin Deshnande. M.S, Tetrahedron

Lett., 1994, 35, 5613

89%

Section 74C

81

Alkylation of Alkenes

2 eq. MesSiCHzMgCl

phwseMe

b l?h-siMe3 5% NiC12(PPh&, DME reflux , 1.5h Hevesi.L,; Hermans,B.; Allard, C. Tetrahedron Left., 1994, 35, 6729 1.0.3 q3-C3HSPdC1)2 , HSiPh2F 0.6 o’-diphenylphosphinobinaphthol Ph-

79%

Ph

derivative

P

20°C , 10h 2. MeLi

Me S iPh2Me

96% (66%ee,S) Hatanaka. Y,; Goda, K.; Yamashita, F.; Hiyama, T. Tetrahedron

NC

/‘Q

Left., 1994, 35, 7981

0

NH 12

NH2

Mn(OAc), , CuOAc ultrasound ,4h

/ Bosman, C.; D’Annibale.

0

47%

A.; Resta,S.; Trorrolo.C, Tetrahedron Bufl+

Left., 1994, 35, 8049

(Ph3SnF2)‘, THF

OTf

Ph Pd(PPh3)4, reflux ,30 min

8-

81% A.&; Barcina, J.O.; Cerezo, A. de F.; Subramanian, L.R. Synlett, 1994, 1047

10% ZrC12(qC&),

1.5 BuMgCl

II, 6h Takahashi. T,; Kotora, M.; Kasai, K. J. Chem. Sot. Chem. Commun., 1994, 2693 ,SiUe3 1. BuLi , THF , -7OOC 2.ZnBr2, -7OOC + 2o”c 3. H30+

t

81%

82

Section 74C

Compendium of Organic Synthetic Methods, Vol9

C$-I&Me#H

, Et3SiH

t

AcH$(H$)4/

SW3

tridecane , di-t-Bu hyponitrite 65% Dang, H.-S.; Roberts,.P,

Tetrahedron

Lett., 1995, 36, 2875

PhSnCl3, aq. KOH ,3% PdC12 *

Br*COOH

Ph*COOH 83%

Rai, R.; Aubrecht, K.B.; Collum. D.B. Tetrahedron

Lett., 1995, 36, 3169

cylization-Diels-Alder

Joumet, M.; B.

m J. Org. Chem., 1995, 60, 6885

Chavan. S.P,; Ethiraj, KS. Tetrahedron

Lett., 1995, 36, 2281

OMe

OMe BF3eOEt2, C&I 12, refk

y 2h

56% Maietich.

G,; Liu, S.; Siesel, D. Tetrahedron

Lett., 1995, 36, 4749

Alkylation

section 74C

83

of Alkenes

Ph 10% Pd(OAc)z ,20% Bu3P Phi , DMF, 100°C, 1Sh

S.-K,; Jung, K.-Y.; Park, C.-H.; Namkoong, E.-Y.; Kim, T.-H. Tetrahedron

Zhang, W.; Dowd. P, Tetrahedron

Lett., 1995,

Lett., 1995, 36, 8539

95% Yu, J.; Cho, H.S.; Falck.

Tetrahedron

Lett., 1995, 36, 8577

. JEt3

, PhMe , reflux

5% RuH2(CO)(PPh& 94% Trost.;

Ixni, K.; Davies, I.W. J. Am. Chem. Sot., 1995, 117, 5371 1. Me3Al,8%

y”

Cl$ZrCpz , DCE ,22OC

2.02 92% (74% ee)

Kondakov,

D.Y.; Negishi.J.

Am. Chem. Sot., 1995, 117, 10771

Compendium of OrganicSyntheticMethods,Vol9

84

4

OTf

Draper,T.L.; mv.

Section74D

CO,Et

,5% PdC12(PPh3)2 w 3 LiCl , DMF , 110°C

T&SynZett, 1995, 157 Si(OEt)g

Si(OEth

, toluene,135OC

0

0

Ru(H)2(CO)(PPh&7 2d

%

c

50% Kakiuchi, F.; Tanaka,Y.; Sato,T.; Chatani,N.; Murai. S, Chem. Lett., 1995,

679

1. BC13, CH2C12,O°C PhwPh 2. catechol, PhH 3. PhBr, Pd(PPh& , NaOH Farinola,G.M.; Fiandanese, V.; Mazzone,L.; Naso.F, J. Chem. Sot. Chem. Commun., ph-sMe3

86% 1995,

2523 REVIEW:

“RecentDevelopments andNew Perspectives In The HeckReaction,”Cabri.W,; Candiani,T. Accts. Chem. Res., 1995,

SECTION

74D:

28, 2

Conjugate Reduction of a&Unsaturated Carbonyl Compounds and Nitriles

0

0

2% [Pd(Pt-Bu)(PHt-Bu& 02 9 H2(10 psi) I 4

Me

90%

THFJ3h glassautoclave )

Sommovigo,M.; u.H.Tetrahedron

Lett., 1993,

4

Me

34, 59

OH Eta-

9 ~&oh6

t

ph//co2ph

CO (1 atm), [email protected],3O”C 80%

bh. x; Fujiwara,IS.; Takahashi,S. Bull. Chem. Sot. Jpn., 1993, 66, 978

Section 74D

85

Conjugate Reduction

PhSiH3, 20°C, 16h MOcomplex

..

(62 Schmidt.T, Tetrahedron

38) 95%conversion

Lett., 1994, 35, 3513

NaHTe, EtOH Ph*CHO

w

phmCHO

rt ,5h

>98%

Yamashita.M,; Tanaka,Y.; Arita, A.; Nishida,M. J. org. Chem., 1994, 59, 350 TFA-Et3SiH,30 min -78°C + O°C

zhao, Y.; m.

variousprotonicandLewisacidsused P,; Keo, E.A. Tetrahedron Lett., 1994, 35, 4179

NH4+HC02-, Pd-C

t

25OC,4h

Ranu.B.C; Sarkar,A. Tetrahedron

Lett., 1994, 35, 8649

Bakersyeast, 31°C =, pheNo2 phmNo2 3d . shl&, M..; Yoshida,S.; Kohno,Y. Heterocycles, 1994,37, 553

43%

limonene, 10%Pd/C, reflux 0

o= von Holleben.M.L,; Zucolotto,M.; Zini, C.A.; Oliveira, E.R. Tetrahedron,

0

quant.

o=

6994, 50, 973

Compendium of Organic Synthetic Methods, Vol9

86

Na&Od

, aq. dioxane

,5O”C

PhA

, lh *

ECHO

Section 74E

Phi

ICI-IO selective

reduction

of conjugated

Dhillon. RS,; Singh, R.P.; Kaur, D. Tetrahedron

carbonyl C=C units L&t., 1995, 36, 1107

Sm, 12, MeOH , 1min t Bessho,K.; Yanada,K. Synlett,

a;

C02Me

ph//C02Et

97% 1995,

443

C02Me

BER-CuS04, MeOH, rt

BER = borohydrideexchangeresin Sim, T.B.; Yoon. N.M,SynZett,

1995,

94%

726

NaBHeBiC13,95%EtOH t

wC02Et Ren,P.-D.; Pan,S.-F.; Dong, T.-W.; Wu. S.-HJynth.

CO2Et 98%

Commun., 1995, 25, 3395

0

0

Bakersyeast

,; Saitou,K.; Hida,K.; Ohno,A. Tetrahedron

SECTION

Asymmetry, 1995, 6, 2143

74E: Conjugate Alkylations

Ranu. B.c; Saha,M.; Bhar, S. Tetrahedron

L&t., 1993, 34, 1989

Section 74E

Conjugate Alkylations

PhS-

b

0’ Li+

EL CH2C12 2d, -78OC

6

‘t,

CO2Me

87

C02Me

6

SPh + 2

(15 Corey. E.J,; Houpis, I.N. Tetrahedron

Lett., 1993, 34, 24k

P 1. PhMgBr , CuBr*SMez

h Tv

2.NBS,THF,-78°C

*

0

Li, G.; Jarosinski,M.A.; J-In&y. V.J, Tetrahedron Lett., 1993, 34, 2565 0

PhguLi , THF , -78OC + TMSCl + TMSCN ; James,B. Tetrahedron

81% 83%-k

Ph

Lett., 1993, 34, 6689

h

3 eq.mSnBu3 0.05(Bu$n)z 6 eq.PhSCH(OMe)z 0.3 M PhH, hv (sunlamp)

ea

20%

Me

69%

OMe

(8: 1 transxis)

mk. G&; Kordik, C.P. Tetrahedron Lett., 1993, 34, 6875

I

1

Me(Boc)NCHzSnBu$s-BuLi TMEDA , CuCN, TI-IF

er. m;

Alexander,C.W. Synlett, 1993, 407

&

98% NMeBoc

Section 74E

Compendium of Organic Synthetic Methods, Vo19

88

Et

$

Et 9 Eu( tfc)3 MS , Ccl,, -33OC, 72h

-*

71% (25%ee)

Eu(tfc)3 = [tris-(3-trifluoromethylhydroxymethylene)-d-camphorato] europium (III) Tetrahedron L&t., 1993, 34, 7649 Bonadies, F.; Lattanzi, A.; Orelli, L.R.; Resci, S.; Screttri.

1. BnOCH~CH+CH/Cp$Zr(H)Cl 2. MeLi , Me$u(CN)Liz

81% rnshutz.R.H; Wood, M.R. J. Am. Chem. Sot., 1993, 115, 12625 0 -3

1. Ni(aca& 2. -w

80% Eshelby,J.J.; Crowley, P.J.; Parsons.P.J,Synlett, 1993, 279 1. Me2CuLieLiI

Bu

/-co2Et

*

2. MeOTf Amdt, S.; Handke,G.; Krause.N, Chem. Ber., 1993, 126,251

4

SO2Ph –

1. t-BuBr , Cr(en)2+2 , DMF ,4h * 2.H20

t-Bu

78%

en = ethylenediamine Tashtoush,H.I.; hstmann. R, Chem. Ber., 1993, 126, 1759

S02Ph

Section 74E

Conjugate AIkylations

89

Ph$b , cat. Pd(OAc);! 0

AgOAc , AcOH ,25OC

Cho, C.S.; Tanabe, K.; Uemura.

Tetrahedron

Ph

Lett., 1994,

0

1275

35,

41%

3 eq. SmI2,THF ,-78°C

Trivellas,A. Tetrahedron Lett., 1994, 35, 1627

-E.J.;

cat. Pd(OAc)z, NaOAc , Id cat. SbC13,AcOH ,25OC *

‘“(‘rf

88%

0

Ph Cho, C.S.; Motofusa, S.; IJemura.S, Tetrahedron Lett., 1994, 35, 1739 r

0

Me02

3 eq.Me$iSnBu3,2 eq.CsF DMF,rt, lh Br Sate,H.; Isono,N.; Okamura,K.; Date,T.; Mori. M, Tetrahedron

Lett., 1994, 35, 2035

MeTi(OiPr)dMgCl , TI-IF Ni(acac)z, -15OC + rt

Bs.; 6075

.

85%

Kabbara,J.; Nickisch,K.; Neh, H.; Westermann, J. Tetrahedron Mt., 1994, 35,

90

Compendium of Organic Synthetic Methods, Vo19

Section 74E

t-BuHgCl , Et3SiH , DMSO ==c

) dark, hv (sunlamp) -35OC , llh Russell. G.A,; Shi, B.Z. Tetrahedron Lett., 1994, 35, 3841 C02Et

Et$i

A

C02Et 93%

iPrCH0, LiNO3, aq.MeCN e’ C02Me +QL 2 34% UT.; Soejima,T.; Takigawa,K.; Yamaguchi,Y.; Maekawa,H.; I(ashimura. S, Tetrahedron Lett., 1994, 35, 4161 Y

C02teBu 1. BuLi, m -100°C + 3o”c

,C02t-B :: = t =

2. H-20

u

70% +

otherisomers

CookeJr.. M.P,; Gopal,D. Tetrahedron

Lett., 1994, 35, 2837

PhCHO, Ph2C0 hv

Kraus.G.A,; Liu, P. Tetrahedron

69%

Lett., 1994, 35, 7723

MeMgCl , CeC13,THF

Bli.

G,; Bosco,M.; Sambri,L.; Marcantoni,E. Tetrahedron Lett., 1994, 35, 8651

Conjugate Alkylations

Section 74E

wey.

a, Hajra, S.; Ghorai, M.K. Tetrahedron

91

Lett., 1994,

35, 7837

MeO&

Bu$nH

COzMe

.

(1 Miura,

Iondo, T.; Hosomi. A, Tetrahedron

0

$

+

, PhH

BuC=CH , PhC=CSnEtj

Wl

W-I

11

1) 54%

Le ‘tt., 1;94,35,9605

, Me&Cl

Ni(acac)z , Dibal , THF , rt ,2h

%A

80% (>95:5 E.-Z) Ikeda, S.; &to.

Y, J. Am. Chem. Sot., 1994,

116,

5975 CHO

I

94% (93:7 1,4: 1,2) Kabbara. L; Flemming, S.; Nickisch, IS.; Neh, H.; Westermann, J. Synlett, 1994, 679 Et2Zn , MeCN , 1.5% NiC12 , -3OOC phL

ph

309’ chual pyrrolidine 0

l

*Phuh 75% (82% ee , S)

Asami. MJ Usui, K.; Higuchi, S.; Inoue, S. Chem. L&t., 1994,

297

Compendium

92

Ph

Section 74E

of Organic Synthetic Methods, Vol9

Z

Li

Y CH2CI;!

99% AI(OAr)3 , -78OC , lh

I

Ar = 2,5diphenylphenyl Maruoka,

Ph

K.; Shimada, I.; Imoto, H.; Yamamoto. H, Synlett, 1994, 519 PhMezSi

0 HSiPhMe2 , toluene , 1 10°C A

-N

*

[Rh2(oAc),l

dNJl

I I Bn Bn u T,; Oda, T.; Kimura, F.; Onishi, H.; Kanda, T.; I(;ito. S, J. Chem. Sm. Chem. Commun., 1994,2143 1. PhMe#Li ph&C02Me

Crump, R.A.N.C.; wing.;

87%

, Me$Zn , THF/toluene , O°C

2* aq* NH4C1

CO2Me

98% 73% using cuprate Urch, C.J. .I. Chem. Sot., Perkin Trans. l., 1994, 701

5% CuBr , THF , TMSCl ,4h AlMe

, 10% solution in hexane

96% Kabbara. J,; Flemming, S.; Nickisch, K.; Neh, H.; Westermann, J. Chem. Ber., 1994, 127, 1489 t-Bu

t-Bu (t-Bu)2Cu(CN)Li2

t-Bu w

C02Et Gerold, A.; .Krause. N, Chem. Ber., 1994, 127, 1547

quant. 111111111 CO2Et

Section 74E

Conjugate Alkylations

93

0

, DME ,0.3h

-A

C02Et

B

.

LiOH , Hz0

96% FJ Forcellese, M.L.; Locati, L.; Screttri, A.; Scolamiero, C. Guzz. Chim. Ital., 1994,

124,467

PhBr, NiBr2, e’ *

-/c”u

63%

phwco2Et

3 H20, DMF-Py , 80°C Bumr , Bu&I Condon-Guegnot&; Leonel,E.; N&l&ec, J.-Y.; P&ichon,J. J. Org. Chem., 1995, 60, 7684 OSiMe3

0 5 M LiClOd, ether

Sarawathy,V.G.; Sankararaman.J.

70% Org. Chem., 1995, 60, 5024

t-BuZnBr , THF/pentane, -3OC 2 TMSCl , 1.5BF3aEt2 Hanson,M.V.; Rieke,

J. Am. Chem. Sot., 1995, I 17, 10775

iPr1, Bu$nH , Yb(OTf)3

t

CH2Q/hexaneKHF . . Slbl. M&; Jasperse, C.P.; Ji, J. J. Am. Chem. Sot., 1995, II7, 10779 neatAl(C3H7)3,5% CuBr Ph& w;

Flemming,S.; Nickisch,K.; Neh, H.; Westermnn,J. Tetrahedron,

76% 1995, 51, 743

94

Section 74F

Compendium of Organic Synthetic Methods, Vo19

1. &D

,O”C,hv

2. LTA , PhH , heat

Barton, D.H.R.; Chem, C.-Y.; Jaszberenvi. JCs, Tetrahedron,

1995,

C02Me 98~25% 51, 1867

R.-S)

61%(80%ee;10:90

Wu, J.H.; Radinov, R.; Porter. N.A, J. Am. Chem. Sot., 1995, 117, 11029 REVIEW:

“Intramolecular MichaelandAnti-MichaelAdditionsto Carbon-Carbon Triple Bonds,”Rudorf, W.-D.; Schwarz,R. Synlett, 1993, 341 SECTION

74F:

Cyclopropanations, SO2Ph

including Halocyclopropanations

‘CH(SOMe)2,DMSO 99% 20°C, 15min

J-E,; Lofstom,C.; Juntunen,SK. Tetrahedron Lett., 1993, 34, 2007 N2CHC02t-Bu, CH2C12

/,%, + ,,+’A *,%, ‘Cod-Bu ‘h ‘C02t-B u . (86 . 14) 75% 92%ee Ito, K.; Katsuki.T, Tetrahedron Lett., 1993, 34, 2661 CuOTF-biarylamine ligand -,PP

C&I, CrCl$Fe

02Et C02Et

Hu. C-M.; Chen,J. Tetrahedron

Lett., 1993, 34, 5957

89%

Section 74F

Cyclopropanations

95

70%

Kreif. A; Dubois, P. Tetrahedron

Lett., 1993, 34, 2691

Ph

P Bu$nN(Et)CO2Me,DCE

(93:7 1,2-tranxcis) Shibata,I; Mori, Y.; Yamasaki,H.; Baba,A.; Matsuda,H. Tetrahedron Lett., 1993, 34, 6567

Ph

h

bis-Rh catalyst, styrene

t 0 . Davies.;

L4 = = Eo,?Me

63% Hutcheson,D.K. Tetrahedron

Ph +

9O%ee

Lett., 1993, 34, 7243

1.NBS, DMSO ,5 min ,,il/v/

::::;:H

*

p Kd’

Dechoux,L.; Ebel, M.; Jung,L.; Stembach.J.F, Tetrahedron

L”ToEt 10%Pd(PPh3)4,DMF ,7h

)

H g2%

(>99: 1 cis:trans)

Lett., 1993, 34, 7405

;

0 Ogoshi,S.; Morimoto, T.; Nishio, K.; Ohe, K.; Murai. S,J. Org. Chem., 1993, 58, 9

gg%

96

Compendium of Organic Synthetic Methods, Vol9

..

(97

.

Section 74F

3)

84%

avres.H.ML; Huby, N.J.S.; CantrellJr., W.R.; Olive, J.L. J. Am. Chem, Sot., 9468

1993,

115,

CrC12- DMF ,3h Bu

CHO 32%

Montgomery,D.; Reynolds,K.; Stevenson.P,J. Chem. Sot. Chem. Commun., SO2Ph

LiCH(SPh)S02Ph,THF

/

SPh

-78OC + O°C

t

1993,

363

PhS Isc-

81% Bailey, P.L.; Hewkin, C.T.; Clegg,W.; kkson. R.F.W, J. Chem. Sot., Perkin Trans. I., 1993,577

Me I

0-

[email protected]

Na+%H(C02Me)2,TI-IF-HMPA -70OC + O°C ,3h

C02Me 63%

Watanabe,Y .; Ueno,Y .; m.

T, Bull. Chem. Sot. Jpn., 1993, 66, 2042 CH212,Zn , Et20 40°C, 8h Pb , Me$iCl

SK.;

Kakiuchi,T.; -0.

Ic J. Org. Chem., 1994, 59, 2671

97%

Section 74F

Cyclopropanations

97

PhS,

b @Ylr::~~~: 302Me Mac 50%

C02Me

Denis,R.C.; Gravel. D, Tetrahedron Lett.,

35, 4531

1994,

(2.7 OH

Bu$n ai

2 [email protected], CH& CH$lz-hexane, -2OOC NHSO&H,pNo,

0

BGn, –

%, /

#H ++

HA_

OH

+ NHS02-C6H4p-NO2

86%ee(2S,3R),94% Imai, N.; Sakamoto,K.; Takahashi,H.; Kobavashi,S, Tetrahedron Lett., 1994, 35, 7045 1. PhCHN2 2. PhCH=CHz, rt , 12h

cp OC-Fe/ oc

-4

Seitz, W.J.; Hossain.M.M, Tetrahedron

80% (96:4 cixtrans) Lett., 1994, 35, 7561

MezN

Ph

&pNMe2 + “)7

1. PheOH

Ph

0/

0 B Bu

w PhvOH

2.2.2 Zn(CH21)2 >95%(29:1)

Charette.A.B,; Juteau,H. J. Am. Chem, Sot., 1994, 116, 2651 Et$n , CH212,CH& hexane, -2OOC

Ph a

Ph-oH

Hs s: a H

,SO,Ph

OH

N ,B-iBu N ‘SO

quant.(76%ee) Ph

Imai, N.; Takahashi,11.;Kobayashi.S, Chem. Lett.,‘1994,

177

98

Compendium

of Organic Synthetic Methods, Vo19

Section 74F

Ph Ph ’ Br

Ph

[email protected]

3

0 +

C&03, 7o”c DME , trace water

Ph

Me3Si

Y.-z;

..

8) 93% MesSi Tang, Y .; Zhou, Z.-L.; Xia, W.; Shi, L.-P. J. Chem. Sot., Perkin Trans. I .,

1994,893

3-pentanone/LDA ,

THF

*

S02Ph Ericsson, A.M.; Plobeck, N.A.; mkvall.

62% J.-E. Acta Chem. Stand. B., 1994, 48, 252

Zn ClMe2SiCH$H$iMe2Cl

Mo(.herwell.

W.B,; Roberts, L.R. Tetrahedron

L&t., 1995, 36, 1121

2 Ti(OiPr)d 4 iPrMgBr -45OC +

0°C 93% (58:42

Kasatkin, A.; Sate.

PhaOH

Tetrahedron

Lat., 1995,

36,

trans:cis)

6079

l.Zn(CH$)2 2. -78OC -+ -2OOC 3. TiQ

*

ph-YoH 90%

Charette.,

Brochu, C. J. Am. Chem. Sot., 1995,

117, 11367

Section 75

Alkyls from Misc.

99

5% semi-corrin Cu complex , DCE 23OC

57% (95% ee) Pique, C.; Fahndrich, B.; pfaltz. A, Synlett, 1995, 49 1 1. XX12 , CC14, reflux 2. NaI04 , 0.1 RuC13

85%

3. Li 5% DTBB , THF 4. H20 Guijarro, D.; Yus. w Tetrahedron,

Ar

Ar = 4- t-bu tylphenyl 1995, 51, 11445

REVIEW:

“The AsymmetricCyclopropanantion of Acyclic Allylic Alcohols:Efficient Stereocontrol with IodomethylzincReagents,”w. A&; Marcoux, J.-F. Synlett, 1995, 1197

SECTION

75:

ALKYLS, METHYLENES AND ARYLS MISCELLANEOUS COMPOUNDS

~co2MhMe#-~-~~2~(OAc)~

as.

.

LEMe

Y,; Planchenault, D.; Weber,V. Tetrahedron Lett., 1994, 35, 9549

SOzt-Bu

FROM

73%

Ph

2 PhMgBr,5% NiC12(PPh&

77%

Clayden,J.; Cooney,J.J.A.; Julia. M cJ. Chem. Sot., Perkin Trans. 1.) 1995, 7 REVIEW:

“OrganonickelChemistryin OrganicSynthesis.SomeApplicationsof Alkyl and MetalacyclicDerivatives,”C&npora,J.; Paneque, M.; Poveda,M.L.; Carmona.E. Synlett, 1994,465

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

100

Compendium of Organic Synthetic Methods, Vol9

CHAPTER

6

PREPARATION

SECTION

Section 77

OF AMIDES

76: AMIDES

FROM ALKYNES 0.3 Iu1&0)16, co, Hz0 dioxane , NEt3 , 175OC Ph Ph

Hirao, K.; Morii, N.; Joh, T.; Takahashl. . S, Tetrahedron

SECTION

77: AMIDES

FROM ACID DERIVATIVES 1. SnFJ(TMS)2]2

OH Bumell-Curty,

2.

C

C.; lXosw Tick,

Lett., 1995, 36, 6243

, THF , rt Pa

NNH

‘N

7 14h

a

89%

Tetrahedron

Lett., 1993, 34, 5193

Li , Me3SiCl CsF’N2

)

+

pANH

iplq.ll

2

Kawaguchi,

C&I17NH2, W-J

17CWH

0

180°C, 30 min t C8h

. SIC. B&;

H

77% M.; Hamaoka, S.; Mori. M. Tetrahedron L&t., 1993, 34, 6907

NHC8H17

98% Zdravkovski,

2. Synth. Commun., 1993, 23, 2761

11%

Section 78

Amides from Alcohols

101

Cl

Ph

NMM , PhCl , mrcrowave *

f

N

75OC ,2 min

Me

.

(20 Bose, AK.; Banik, B.K.; Manhas. MS, Tetrahedron

80) no yield

Lett., 1995, 36, 213 Ph

PhCH-NPh , toluene , Bufl 40% (5:95 cis:trans) Ph Browne, M.; Burnett, D.A.; Caplen, M.A.p; Chen, L.-Y.; Clader, J.W.; Domalski, M.; Dugar, S.; Pushpavanam, P.; Sher, R.; Vaccaro. W,; Viziano, M.; Zhao, H. Tetrahedron Lett., 1995, 36,2555 -C02H

,CWl;!

‘z ;;iPPb

. Frayen. P,Synth.

t

bCONHBn

2

98%

Commun., 1995, 25, 959 1. NsCl , NEt3 , DMAP/MeCN

, rt

0

+

PhCOOH 2. PhNH;! , rt

NHPh

Is,e. JC,; Cho, Y.H.; Lee, H.K.; Cho, S.H. Synth.Commun.,

SECTION

78: AMIDES OH

FROM

ALCOHOLS

1995, 25, 2877

AND THIOLS

CoC12, Ac20, MeCN *

Mukhopadhyay,

M.; Reddy, M.M.; Maikap, G.C.; w.

-(=)-/OH

MeCN , BFyOEt2

Firouzabadi.

LNHAc

J, J. Org. Chem., 1995, 60, 2670

w-

H,; Sardarian, A.R.; Badparva, H. Synth. Commun., 1994, 24, 601

92%

102

Section 81

Compendium of Organic Synthetic Methods, Vol9

SECTION

79: AMIDES

FROM

ALDEHYDES

NO ADDITIONAL EXAMPLES

SECTION

80:

AMIDES ARYLS

‘-(=)

FROM

ALKYLS,

PPA , AcOH , NH20H*HCl

METHYLENES

AND

‘-0

*

llO°C , 14h

80% Cablewski,T.; Gurr, P.A.; Raner,K.D.; S

SECTION

81: AMIDES

FROM

Org. Chem., 1994, 59, 5814

C&J.

AMIDES

Conjugate reductions of unsaturated amides are listed in Section 74D (Alkyls from Alkenes).

oJ-q// 1,,,,,,, A H

Wei, Z-Y.; Knaus.

Tetrahedron

Lett., 1993, 34, 4439

2.1 TBSOTf ,23OC 4.2 NEt3 , 1.75h

Ph J

R *

N/ I

Phd/Me

Me 75%

2.1 TBSOTf ,23OC 4.2 collidine ,2h

&&

91% (>99%ee)

MeOH

H

Ph

J 49%

G.E.; McHardey,S.F.; Murry, J.A. Tetrahedron

PhI(OAc)2,

A! I

KOH

N/

Me

I

cH2oTBs

Lett., 1993, 34,6215

72% NHCO2Me

Vaid, R.K.; P&ash, 0.; Tuladhar,SM. J. Org. Chem.,

Section 81

Amides from Amides

PhMgBr , THF

OEt H Wei, Z.Y.; Knaus.

A

Ph

103

H

78%

Org. Prep. Proceed. Int., 1993, 25, 255

1. 2 eq. s-BuLi, (-)-sparteine NHMe 2. Me1

Beak. P,; Du, H. J. Am. Chem. Sot.,

1

NHMe 84%(78%ee)

1993,

115, 2516

0

4.2 eq.CuBrz*LiOt-Bu

77%

*

Ph rt ,6h NH2 Yamaguchi,J.; Hoshi,K.; Qkgla. T, Chem. Lett.,

5) c>, 0

1993,

PhHNJL

Ot-Bu

1273

, acetone, O°C

CL N N 0 I I H OH Nesct,S.M.; Benneche,T.; Undheim,K. Acta Chem. Scand. B., 1993, 47,

71% 0 1141

CF3S03H, CH2C12 H

0.75h , 20°C

m

C.&l,; Fallah,A. Tetrahedron

&-H

Lett., 1994, 35, 293

DkE

*

4-K;

DIAD = diisopropylazodicarboxylate 0 Ww.

M.A. Tetrahedron

Lett., 1994, 35,665

91% (+ 4% lactone)

104

Compendium

of Organic Synthetic Methods, Vol9

Section 8 1

1. Br;! 2. NEt3 3. BnNH2

n B N

4. Mg(OMe)z

tier.

P,; Dogan, 0.; Pillai, S. Tetrahedron

H

Lett., 1994, 35, 1653

Axon, J.; Boiteau, L.; Boivin, J.; Forbes, J.E.; md.

Hoffman.V,; 35,323l

(s)

*Y 86×79%

1. (PhCO)zO , PhH , reflux 2. Bu$nH , AIBN , PhH

BnI-IN

P

, MeOH

02Me

Me

67%x”high yield” Lett., 1994, 35, 1719

SZ, Tetrahedron

iPrOH , 80°C, lh

d I OTf Nayyar, N.K.; Shankweiler,

CH20iPr 85%

J.M.; Klinekole

H III, B.W. Tetrahedron

C7H &HO, Hz, 40 bar Pd/C-Na2S04, EtOAc

0

0

1ooOC H Fache, F.; Jacquot, L.; J,eme.

Ph-NVCI

93%

w17

M, Tetrahedron

L&t., 1994, 35, 3313

s-BuLifIMEDA I Boc

Lett., 1994,

, THF

a

Ph 4

-78OC, 5h

Beak. P,; Wu, S.; Yum, E.K.; Jun, Y.M. J. Org. Chem., 1994, 59, 276

N I Boc

82%

Section 81

Amides from Amides

105

PhCHO , PPE , 60°C, 16h

H N’

51% * I PPE = polyphosphoric ester ci Ph Marson. CM,; Grabowska, U.; EaIlah, A.; WaIsgrove, T.; Eggleston, D.S.; Baures, P.W. J. Org. Chem., 1994, 59, 291 NH2

S Me N’

1. 1.3 eq. POC13,

-78OC

2.3.5 eq. TM&S

, -78OC +

Me N’ rt ,4h

91%

* c ei Smith, D.C.; Lee, S.W.; Fuchs. P.L, J. Org. Chem., 1994, 59, 348 0

0

BnNH2, AlC13 , 90°C >

NHBn

NH2

67% Bon, E.; Bigg. D.C.H.: Bertrand. G, J. Org. Chem., 1994, 59, 4035

yx N I

1.2 s-BuLi/2 TMEDA THF , -78OC, 8h Ot-Bu

2. BuI

CH3

Snieckus. V,; Rogers-Evans, M.; Beak. P,; Lee, WK.; 1994, 35, 4067

0 -Y

A N Ot-Bu I CH2Bu 70% Yum, E.K.; Freskos, J. Tetrahedron L&t.,

Bu$nH , cat. AIBN (addn over 4 h) degassed cyclohexane –

(Do

Ph Callier, A.-C.; Quiclet-Sire,

B.; Zard. S.2, Tetrahedron

66% Lett., 1994, 35, 6109

Me

106

Compendium of Organic Synthetic Methods, Vol9

Bu$nH,

Section 8 1

AIBN

PhH (OSM) Keusenkothen,

P.F.; Smith. M.B, J. Chem. Sot., Perkin Trans. I., 1994, 2485

Ts I N

iPrMgC1, THF , O°C ,6h

/

4J4 *‘Ph

. . oshlmuu. 3465

. 57) 63% (45 A, ; Abe, H.; Hirosawa, C.; Tamao, K. J. Chem. Sot., Perkin Trans. I., 1994,

anek- E,; Wuonola,M.A.;

NH2

Harlow, R.L. J. Heterocyclic

65% x low yield Chem., 1994, 31, 1251 H I NN

1. B tCH20H

2. CH2=CHCH2SiMc3 BF3eOEt2 63% 0 R… menko. A.V.. . La n g. H, J. Org. Chem., 1995, 60, 4002

0

a V-bhBr OMe

I

/

N’ I

Bu$nH , AIBN , PhH reflux ,8h (syringe pump, 7h) *

~;~;NHco2Mx;:~ 2

co$k 30%

Lee.;

Whang,I-IS.; Chung,C.K. Tetrahedron

Mt.,

1995, 36, 913

360/ 0

co2M

Section 8 1

Amides from Amides

-L

(BnNEt&MoQ

107

, CHg12

82%

)

Ph

-78OC * rt ,30 min me2 Ilankumaran, P.; Ramesha, A.R.; Chandrasekaran. S, Tetrahedron L&t.,

me2

1995,

36, 8311

1.2.2 eq.BuLi , THF , -78OC+ 0°C 0 2.

0

Ph

N’

I d

NHMe 4

I

3. H30+ 4. Me$iCl , NaI , MeCN

/

WY. Pts, Tetrahedron

Lett., 1995,

/

Me

Ph

A

Ph 75%x92%

36,493

2 SnC12,2KI CH2C12 , rt , 12h N-(f6Hll

53% + 10%benzophenone Qmoka

T,; Iwama, T. Tetrahedron

Lett., 1995,

36, 5559

HC=CCH2Br,DMWDMF , NaH LiBr , O°C + rt THPO Liu, H.; Ko, S.-B.; Josien,H.; Curran.D.P, Tetrahedron

Lett., 1995,

36, 8917

Ph

Ph Ph

Mn(OAc), AcOH

D’Annibale,A.; Resta,S.; Trogolo,C. Tetrahedron

Lett., 1995,

36, 9039

87%

108

Compendium

42

of Organic Synthetic Methods, Vol9

Section 82

2% Rh#SMEPY)4 0

cwkt

N -b

Y Doyle. M.P,; Kalinin,

0

70% (96% ee)

cm2

A.V. Synlett, 1995, 1075 SPh

MeS

&SPh

neat, rt Id Ar = 4-methoxyphenyl

66%

Ar . x; Nakaharu, T.; Nishimura, M.; Nishikawa, A.; Kameoka, C.; Ikeda, M. Tetrahedron, m. . 1995, 51, 2929 Ph Bu$nH, Ph

I

AIBN

Ph

*

+

toluenhe , reflux

Me bile

Me

47% 12% Sato, T.; Chono, N.; Ishibashi, H.; Ikeda. M, J. Chem. Sot., Perkin Trans. I., 1995, 1115

@O ,SO2Tol

Ph

Ph

Me$GCHC02Et

41%

N -7

. u-. UJt;

SECTION

b/ TolO# Arora, A. J. Chem. Sot., Perkin Trans. I., 1995, 2605

82: AMIDES

FROM

AMINES

NaB03a4 Hfi

P L -N-Ph Nongkunsam,

C02Me

, CF3C02H

80°C

P.; Ramsden. CA, Tetrahedron

+

H

Lett., 1993, 34, 6773

B

N

/

Ph 51%

Ph

Section 82

Amides from Amines

109

0

NHBn

Sn[NUMS)212 9hexme 9fi CO2Me

C3H

pivalic acid

A

5r

C3H7

N

P

Bn

89% Wang, W.-B.; w

J. Am. Chem. Sot., 1993, 115, 9417 NCCH2CH0,

c8H

17-NH2

Duetsch, J.; Niclas. H.-J,Synth.

r-t, 6h

) C&I 17-NHCH0 Commun., 1993, 23, 1561

78%

1. N-cyclohexyl-N’,N’,N”,N”tetramethylguanidine , pyridine toluene , CO2 , – 10°C 2. toluene , SOCl;! , -1OOC 77% McGhee. W.D.; Pan, Y.; Talley, J.J. Tetrahedron

1. 2eq.

Let?., 1994, 35, 835

R pkPhP Cl

3eqNEt3,THF

67%

2. excess NaH Osbom, H.M.I.; Cantrill, A.A.; Sweenev. J.B.; Howson, W. Tetrahedron

Let?., 1994, 35, 3159

xylene , 150°C, 3h NHBn -Gee.

c), N I Bn

0 93%

DLL; Ramaseshan, M. Synlett, 1994, 743

oc

NHBn

CO, MeCN Pd(PPh3)4, NBu3

OTf

Qiso. G.T,; Meyer, A.G. Tetrahedron,

quant. 1995, 51, 5585

110

Compendium of Organic Synthetic Methods, Vol9

C3H7wmt*

co [email protected]

9dPPP )

Section 83

C3~7Aqqmt2 0

b&&&.

. S.-L; Imada, Y.; Nishimura, K. Tetrahedron,

SECTION

83: AMIDES

FROM

78%

1994, 50, 453

ESTERS ,0C02t-B u

H-N moAc

OCOzt-Bu

C02t-Bu

I

K2CO3, IT, Id

mNxC02t-Bu

77% . J-P,; Thorimbert,

S.; Touzin, A-M. Tetrahedron

L&t., 1993, 34, 1159

h

2 eq.Sn[NTMS2]2 2 eq.Me2NCH2CMe20H Ph-CO2Me

*

2 eq.PhCHMeNH2

dyA H

Wang,W.-B.; Restituyo, J.A.; Roskamo. E.J, Tetrahedron

Ph LA

0

1.5SnFJ(TMS)& , THF

0 OMe

97%

L&t., 1993, 34, 7217

*

1.5Et2NHaHCl,rt , 18h

Ph 3

mt2

52% Smith, L.A.; Wang, W.-B.; Burnell-Curty, C.; Roskamn.E.J, Synlett, 1993, 850 0

iPrNH2, t-BuOH ,1.5d 0-

Chen.S.-T; Chen,S.-Y.; Chen,S.-J. Tetrahedron 0 C3H

7A

*

25OC

I H

NaEtzAl(Bn)z, toluene OEt

reflux , lh

69%

Lett., 1994, 35, 3583

0 * C3H

72

NHBn 93%

Sim, T.B.; Yoon. N.M,SynZett,

1994, 827

Section 85

/ PMP

Amides Tom Halides

r

Ph

I N

)

111

(Lp+

]

(;p

2. NEt3 , CH2C12

PMP = 4-methoxyphenyl

. 30) 99% (70 Annunziata. R,; Benaglia, M.; Cinquini, M.; Cozzi, F.; Ponzini, F.; Rimondi, L. Tetrahedron, 1994, 50, 2939

0 A

1. BC13-SMe2 SPY

Ph/i

p-l =-

Me

Ph

NMe2

74% (78%ee)

*

2. O*

ph3N-PMP

PMP

PMP = N-4methoxyphenyl Annunziata,R.; Benaglia,M.; Cinauini.M.: Cozzi. F, Tetrahedron Lett., 1995, 36, 613

SECTION

84:

AMIDES FROM THIOETHERS

ETHERS,

EPOXIDES

AND

NO ADDITIONAL EXAMPLE!3

SECTION

85: AMIDES Br SiMe3

FROM

HALIDES

1.Mg

AND SULFONATES

m

2. PhNCO

83%

Co& Jr.. M.P,; Pollock, C.M. J. Org. Chem., 1993, 58,

-MgBr

c1’NMe2

+ bme2

cat. NiClz(dppe), THF vrt Babudri,F.; Fiandanese, V.; Marchese.G,; Punzi, A. Synlett,

1994,

719

90%

112

Compendium of Organic Synthetic Methods, Vo19

Section 87

1. CS2, THF PhMgBr

2. BtS02CF3

63%

w

3. BuNI&

. ~A.R.;

SECTION

Bt = benzotriazol-l-y1 Moutou, J.-L.; Yang, 2. Synlett, 1995, 99

86: AMIDES

FROM

NHBu

HYDRIDES

NO ADDITIONAL EXAMPLES

SECTION

87: AMIDES

FROM

Me02C-

aldehydes canalsobe used

KETONES

NH2

TEA, N~BH(OAC)~ DCE , rt ,45h

t

00-b 92%

bdel-Manid. A.F,; Harris,B.D.; Maryanoff, C.A. Synlett, 1994,81 OTIPS

1. 10eq.TMSN3 2 eq.PPTS CH2C12,rt ,2d 2. UV , 0°C , lh 79~89%

Evans. P.A%;Modi, D.P. J. Org. Chem., 1995, 60, 6662

Milligan, G.L.; Mossman,C.J.; Aube, J. J. Am. Chem. Sot., 1995, 117, 10449

1. NI$OSO3H, SiO2 2. Hz0 , microwave Laurent,A.; Jacquault,I?; Di Martino, J.-L.; Hamelin.J, J. Chem. Sot. Chem. Commun., 1995, 1101

Section 89

Amides from Alkenes

SECTION

88: AMIDES

FROM

113

NITRILES

UHP , cat. K2CO3 , aq. acetone N

PhCN

P

rt, lh

UHP = urea-hydrogen peroxide adduct Balicki. R,; Kaczmarek, L. Synth. Commun., 1993, 23, 3149 H

L

H

Mn02, SiO2, hexane

CN P Breuilles,P.; Leclerc,R.; m.

rt,lod

*

D, Tetrahedron

92%

Pu

Lett., 1994,

NH2

35,

1401 0

Al203 (neutral), 60°C, Id

70%

CN

t * w NH2 Wilgus,C.P.; Downing,S.; Militor, E.; Bains,S.; Pagni. R&k: Kabalka. GW, Tetrahedron Lett., 1995, 36, 3469

SECTION

89: AMIDES

FROM

ALKENES

TsN=IPh, Mn salencatalyst * PhA Ph pyridineN-oxide, MeCN , rt Noda, K.; Hosoya,N.; Irie, R.; Ito, Y.; Katsuki. T, Synktt, 1993, 469 1. PhI=NTs, Cu(OTf)2, MeCN e 2.0.1 M NaOH

Ts

34%

N-Ts

N d-

77%

JCL; Muldowney, M.P. Synlett, 1995,949

SECTION

90:

AMIDES

FROM

MISCELLANEOUS

COMPOUNDS

BnN=C=O, hv (Pyrex filter) @

42% cr(m3

v. J.H.; Ahmed,G.; Ferguson,M.D. Tetrahedron

L&t., 1993,34, 5397

114

Section 90

Compendium of Organic Synthetic Methods, Vol9

o=

Bu&Re04,

N-OH

CF$03H,

MeNO

*

50% H2NOHaHCl

Narasaka, K.; Kusama, H.; Yamashita, Y.; Sato, H. Chem. Lett., 1993, 489

)iic,

T”Sy

v

+ a

2STMSOTf,CH; 7

202

n=

aux

,O,

Ph

Ph

Pouilhes,A.; Langlois.Y,; NshimyumuKiza, P.; Mbiya, K.; w.

30% (>95:5enbexo) 1,. Bull. Sot. Chim. Fr.,

1993, 130, 304

9 //O

0//

2. 1. MeMgCl BEt3 *

Ph’

3. H2NOS03H Me Huane..-C,; Reinhard,E.J.; Reitz, D.B. Tetrahedron

0 50%

PhHs NH2

Mt., 1994, 35, 7201

hv , hexane, PhNMe2

ipmaJ( = 0.77 Post,A.J.; Nwaukwa,S.; Morrison. H, J. Am. Chem. Sot., 1994, 116, 6439

CO, MeOH, Pd(dpppK129PhH K2C03,160°C

NHCOzMe 59%

MeO$HN02N

Reddy,N.P.; Masdeu,A.M.; El Ali, B.; Alner. H, J. Chem. Sot. Chem. Commun., 1994, 863

Section 90A

Protection of Amides

Ph. 70

Mn(tpp)Cl

, MeCN

3o”c

0

115

Ph.

* P

0 60% tPP = tetraphenylporphyrin Suds. K,; Sashima, M.; Izutsu, M.; Hino, F. .I. Chem. Sot. Chem. Commun., 1994, 949 Montmorillonite

N-OH

K-10, microwave *

NHPh

7 min

Bosch, A.I.; de la Cruz, P.; Diez-Barra,

(17% with heating and no microwave) E.; Loupy, A.; Langa. F, Synlett, 1995, 1259

DMF , POC13, 90°C ,.

N-OH Majo, V.J.; Venugopal,

CHO

0 M.; Prince, A.A.M.;

N-OH

60% Perumal. P.T, Synth. Commun., 1995, 25, 3863 H N

0.2 Bu$lRe04,0.2 CF$OsH MeNO*, reflux ,0.5 NH~OH~HCl

Phx>”

0

CJ Ph Kusama, H.; Yamashita, Y.; Narasaka, K. BuZl. Chem. Sot. J’n., 1995, 68, 373

SECTION

*

90A:

PROTECTION

91%

OF AMIDES

0

0 0

2 Mn(OAc)3.2 H20, EtOH CU(OAC)~~H~O, 55OC 45%

N4

N4

SiMe3

OH Ghosh, A.; MiI&r. MuI Tetrahedron

L&t., 1993, 34, 83

H

SiMe3

116

Compendium

of Organic Synthetic Methods, Vol9

Section 90A

1. AlC13 ,6O”C 2. PhOMe ,6h

Kim, J.N.; Ryu. E.K, Tetrahedron

Mg(ClO&

Boc P Stafford.=; 7873

Lett., 1993, 34, 3567

99% 50°C ,20h * PA NHMe r’ Me Brackeen, M.F.; Karanewsky, D.S.; Valvano, N.L. Tetrahedron L&t., 1993, 34,

Mg(OMeh P

0

, MeCN

, MeOH

0

CO$-Bu Wei, Z.-Y.; Knaus.J Tetrahedron

P –

0 +

H

90%

Lett., 1994, 35, 545 5 eq. Ac20,4% 2.2 eq. Bu$nH

Pd(PPh& , CH2C12

NHOMe AcHN * G 58% o Roos, E.C.; BernaM, P.; Hiemstra, H.: Speckamp. W-N,; Kaptein, B.; Boesten, W.H.J. .I. Org. Chem., 1995, 60, 1733 rt , 10 min

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

Amines from Alcohols

Section 93

CHAPTER

7

PREPARATION

SECTION

91: AMINES

OF AMINES

FROM

ALKYNES

NO ADDITIONAL

SECTION

92: AMINES

ox

SECTION

I

117

93: AMINES

FROM

ACID DERIVATIVES

NO ADDITIONAL

FROM 1. MeLi,

EXAMPLES

EXAMPLES

ALCOHOLS

AND THIOLS

THF

2. PhCN , warm OH Fitzgerald, J.J.; Michael, F.E.; Qlofson. R.A. Tetrahedron

(J-JPh

*

47%

/

L&t., 1994, 35, 9191 Me

1. BuN3, 2.5 eq. TfOH 95% 2. NaBH4 mn.

W.R,

Bu

Fang, W. J, Org. Chem., 1995, 60,496O PhCH2NHTf

, DEAD,

PPh3

PhCHzOH 93% Bell, K.E.; Knight. D.W; Gravestock, M.B. Tetrahedron

==c OH

Lett., 1995, 36, 8681

HNBn2, SnC12, [email protected], THF ,2d

w NBn2

2% Pd(PPh3)4, 50°C

70% Masuvama.

Y.; Kagawa, M.; Kurusu, Y. Chem. L&t., 1995,

1121

Compendium of Organic Synthetic Methods, Vol9

118

SECTION

94: AMINES Me3S’

PhCHO

FROM

ALDEHYDES

-3

Me3SiCl ,29h

Jahn, U.; Schroth. W, Tetrahedron

(t

Section 94

Lett., 1993,

34, 5863

1. C$I 1lCHO , BER , EtOH NH2

Et3NHCl 2. BER , NaOH

* o-

NHCH2C5H1 l

BER = borohydride exchange resin Yoon. N.M.; Kim, E.G.; Son, H.S.; Choi, J. Synth. Commun., 1993, 23, 1595 LiAl(NHBn)d,

89%

ether

25OC, 7h Solladie-Cavallo.

A,; Bencheqroun,

M.; Bonne, F. Synth. Commun., 1993,

23,

1683

1. Bzt-SNH2 , NaOH , EtOH 2. PhSN(TMQ, cat. TBAF , THF Ph

3. Bu$nH

-?B&in,

, cat. AIBN , cyclohexane

CHO

61×69%

J.; Fouquet, E.; Zard. SZ, Tetrahedron,

1994, 50, 1745

1. Me2NH*HCl, Ti(OiPr), EtOH ,25OC, 10h

, NEt3 *

ph-CHO 2. NaBH4,25OC Bhattacharvva,

PhCHO

S, .I. Org. Chem., 1995,

Phw

NMe2

, 10h

95%

60,4928

1. BnNH2, PyeBH3, MeOH MS 481,16h

>

Ph/N-Ph

2.6NHCl 3.8 N NaOH Bomann, M.D.; Guch, I.C.; DiMare. M, J. Org. Chem., 1995, 60, 5995 TsNH2, Si(OEt), , 160°C, 6h > PhCHO Love. BE; Raje, P.S.; Williams II, T.C. Synlett, 1994, 493

PhCH=NTs

I H

87%

68%

Section 96

119

Amines from Amides

BnNH2 , Bentonite , rt ,3h

PhCHO

w

80%

PhCH=N-Bn

ketones can also be used Saoudi, A.; Benguedach, A.; Benhaoua. H, Synth. Commun., 1995,25,2349 Related Methods: Section 102 (Amines from Ketones)

SECTION

95:

AMINES ARYLS

FROM

ALKYLS,

METHYLENES

AND

NO ADDITIONAL EXAMPLES

SECTION

96: AMINES

FROM

AMIDES

C6Hl3

Fisher, G.B.; Fuller, J.C.; Harrison, J.; Goralski, C.T.; Sin Tetrahedron Lett., 1993, 34, 1091

R,

KH , THF , Cp2ZrHC1

JyClOH21 t

PhJL

-2OOC + rt

PlrJ

NwoH21

86%

Schedler, D.J.A.; Godfrey, A.G.; Ganem, B, Tetrahedron Lett., 1993, 34, 5035 1. LiHMDS ; BnBr 2. LiHMDS ; Me1 3. LiA1H4 4. H2, Pd-C

G? Ph 0 Westrum, L.J.; Meyers. A& Tetrahedron

+ H’ 89%

Lett., 1994, 35, 973

Ph Tic13 ,3 eq. CsK Ph

Fs

90% H A; Hupperts, A.; Ptock, A.; Janssen, E. J. Org. Chem., 1995, 60, 5215

H

120

Section 97

Compendium of Organic Synthetic Methods, Vol9

0

A

HBr ,163OC

*

N

H-Nw-ph

NI-IPheHBr

L-l

88% Poindexter. Cr.&; Bruce, M.A.; LeBoulluec, K.L.; Monkovic, I. Tetrahedron L&t., 7331 /sWF3

1994,

35,

t-BuLi , THF , -60°C, 3h t-Bu

52% Bozee-Ogor, S.; SaIou-Guiziou, V.; Yaouanc, J.J.; Handel. H, Tetrahedron L&t., 1995, 36, 6063 Ph 3 Ti (powder), THF, 21h 3 TMSCl , reflux

t

Ph

AN-(

Ph

I

H r. pL; Hupperts, A. J. Am. Chem. Sot.,

1995,

117,

4468

H I

N

S

30%H202, AcOH, 25OC w

Me Grivas, S.; Ronne, E. Acta Chem. Scand. B.,

1995,

49,

H n-

N

Me

85%

225

Related Methods: Section 105A (Protection of Amines)

SECTION

97: AMINES

c

N -Ph

AImena, J.; Foubelo, F.; m

FROM

AMINES

1.5 Li (powder) , TI-IF cat. CteHs , -78OC, 6h 2.H20 M, Tetrahedron

* vNHPh 93%

Lett., 1993, 34, 1649

Section 97

Amines from Amines

PhCHO , TFA

Me H

121

Et$iH , CH2C12, O°C

83%

H

Appleton, J.E.; Dack, K.N.; Green, A.D.; Steele. J, Tetrahedron

L&t., 1993, 34, 1529

9-BBN , THF ,20h *

Wy-”

56%

H ‘Ar Ar = 3,4-dimethoxyphenyl Gaul, M.D.; Fowler, K.W.; Grieco. P.A, Tetrahedron L&t., 1993, 34, 3099

70%

2. H30+ Maye, J.P.; Nerrishi. E. Tetrahedron

L&t., 1993, 34, 3359

?h

Ph

I/ 0 h

A

T

A 10 eq. MeLi, PhH ,5O”C w-

I v H’

I v

+

I-Y

N

NH2

Y >60% Genin, M.J.; Biles, C.; Romero&D.L, Tetrahedron

0

Mt.,

20% 1993, 34, 4301

1. s-BuLi , TMEDA 2. Me1

3. s-BuLi, TMEDA * Mz&’cx N 4. Me1 I Boc I&&. P,; Lee, WK. J. Org. Chem., 1993, 58, 1109

62×41% N

I Boc

Me

122

Compendium

9

of Organic Synthetic Methods, Vol9

Section 97

t-Bu 1.1.5 LDA, THF , O°C 62%

THF, 15h , O°C + rt 3.3 eq. K2CO3, MeOH heat, 3h N.G,; Keppens, M.A.; Stevens, C.V. Tetrahedron

Lett., 1993, 34,4693

2.5 eq. LiBHEt3 , THF , rt 84% (1:l cixtrans) Blough, B.E.; Carroll, F.I. Tetrahedron

0

N

I H Kanth, J.V.B.; Pemv.

aI/

NH2

H L&t., 1993, 34, 7239

2.PhBr,THF,rt,6h l.Li,THF 3. MeOH ; 20% HCl MJ.

)

0

86%

N I Ph

Org. Chem., 1993, 58, 3156 H I

5% Pd(OAc)2, 5% PPh3 100°C ,3.5d, Na2CO3 +65, ’ * Larock. R.C,; Berrios-Pefia, N.G.; Fried, C.A.; Yum, E.K.; Tu, C.; Leong,W. J. Org. Chem., 1993, 58, 4509 I

ONMe

1. w&r
95% 36, 7357

Section 105A

CL

Protection of Amines

139

, DCE , reflux

N Me 2. MeOH, reflux I Bn Yane. B.V,; O’Rourke, D.; Li, J. Synlett, 1993, 195

*

TiC13-Li , THF , reflux ,22h Me2NBn c, Talukdar, S.; Banerji. A, Synth. Commun., 1995, 25, 813

(R

74% N I H

Me2NH

Me

55%

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

140

Section 107

Compendium of Organic Synthetic Methods, Vol9

CHAPTER

8

PREPARATION

3

SECTION

OF ESTERS

106: ESTERS FROM ALKYNES OH

xylenes , 150°C

H OEt

~ 72%

OH Liang, L.; Ramaseshan, M.; MaGee. D.1, Tetrahedron,

SECTION

0

0

1993, 49, 2159

107: ESTERS FROM ACID DERIVATIVES

The following 1. 2. 3.

2x

types of reactions are found in this section:

Esters from the reaction of alcohols with carboxylic acids, acid halides and anhydrides. Lactones from hydroxy acids Esters from carboxylic acids and halides, sulfoxides and miscellaneous compounds 0 0

tiI

0 Li [Binol-AlHOEt] -78OC +

, THF rt –

0 Matsukl.;.

(84% e-e)

Inoue, H.; Takeda, M. Tetrahedron CO2I-r

0

I ti

Lett., 1993, 34, 1167

PhCHzOH ,2,6-lutidine C

k/ Cl 00SfN

Cl

Folmer, J.J.; Weinreb. SM, Tetrahedron

9 C&C12

-78OC + rt Lett., 1993, 34, 2737

C02CH2Ph

81%

69%

Section

Esters from Acids

107

K

141

2

H

Si( iPr),

a

90°C

OH Soderauist, J.pL; Miranda, E.I. Tetrahedron Lett., /

0-S 1993,34,4905

/

C02H

TEOA = triethyl orthoacetate Trujillo, J.I.; Goaalan.AS, Tetrahedron Lett., 1993,

i(iPr)3

93%

C02Et

7355

34,

C&[email protected] , TsOH, neat PhC02H

my.

PhC02C8H17 97% microwave,3 min A,; Petit, A.; Ramdani,M.; Yvanaeff,C.; Majoub,M.; Labiad,B.; Villemin. D, Can. J.

Chem., 1993, 71, 90

Ph-CO

1. NBS CH$I;!, MS 481 O°C, PPh3

2H

2. PhCH20H, Py , lh Sucheta,K.; Reddy,G.S.R.;Ravi, D.; -Q&W.

fd

Ph

phwco2H

~

VPh

Ph 7

x Tetrahedron

98%

0 Lett., 1994, 35, 4415

20%Tic14+ 2 AgC104 Ph+P (ArCO)20 9MS3A Ar = 3,5-trifluoromethylphenyl Shiina,I.; Miyoshi, So.; Miyashita, M.; Mukaiyama,T. Chem. Lett.,

HOqCHz)lo

JL OH

Ph

0 OH

5%TiCLz(OTf)z, (ArCO)20 3 TMSCl , CH2C12 (2 mM) reflux (slowadditionover 5 h)

Ar = 4-trifluoromethylphenyl Shiina, I.; Mukaiyama,T. Chem. Lett., 1994, 677

*

0

90% 1994,

515

A==

0

CJ32ho

83% + 10%diolide

142

Compendium of Organic Synthetic Methods, Vol9

C17H31C~H

*

cat. DMAP , lh

Section 108

C1f131C%cH~H=CH2

85% Akiyama, A.; Konda,Y.; Takayanagi,H.; Harigaya,Y. Tetrahedron Mt., 199% 36,

NK.; 113

Togo. H,; Muraki, T.; Yokovama.M, Tetrahedron

Lett., 1995, 36, 7089

Bu-C=C-H, 100°C,5 eq.NEt3 5% Pd(PPh&t, ZnCl;! 84% Liao, H.-Y.; Chew. E.H, J. Org. Chem., 1995, 60, 3711 Furtherexamplesof thereactionRC02H + R’OH + RC02R’areincludedin Section108(Estersfrom AlcoholsandPhenols)andin Section30A (Protection of CarboxylicAcids).

SECTION

108: ESTERS

FROM

ALCOHOLS

AND THIOLS

Furtherexamplesof thereactionROH + RCO2R’areincludedin Section107 (Estersfrom Acid Derivatives)andin Section45A (Protectionof Alcoholsand Phenols). 1. BuLi, THF, rt PhmOH

;s ph/n/Yco2Et . C02Et 5% Pd(PPh3)4,8h (80:20 E.-Z) 10%PPh3,reflux Star$, I,; Star& I.G.; IWovsky, P. Tetrahedron Lett., 1993, 34, 179

80%

Section 108

143

Esters from Alcohols

OH

&&j)oa.

CL;

3.5 Ca(OC1)2,2

C02Me

AcOH

89%

32MeOH,darkJd MeCN , rt Nice, L.E.; Shaw, A.W.; Nestor, N.B. Tetrahedron

Lett., 1993, 34, 2741

1. sOC12, DMF

4 C 13H27CH20CH0 2. H20 I.; Garcia, B.; MuAoz, S.; Pedro. J.R,; de la Salud, R. Synlett, 1993, 489

CL3H2$H20H Femtidez, tioH

KNOflFyl.25

Hz0

CH2C12,O”C

+ rt

95%

-ON02 95%

Olah. G.A,; Wang, Q.; Li, X.; P&ash,

G.K.S. Synthesis, 1993, 207

1. Cr(CO)9THF,

THF, 55OC t

w. 81%

m.

P,; Rahman, S.; Ward, E.L.M. Tetrahedron

Lett., 1994, 35, 3801

Pb(OAc), , PhH , CO C3H77

OH

Tsunoi, S .; Byu. I.: Son& Hok

m

40°C) Id

N, .I. Am. Chem. Sot., 1994, 116, 5473 NaBrO2, Al203 9 c&cl2

57%

.

T,; Hirano, M.; Iwasaki, K.; Ishikawa, T. Chem. Z&t., 1994, 53

30:1 (2,3-antixyn)

Panek.J.S,; Garbaccio,R.M.; Jain,N.F. Tetrahedron

BuOH ,0.2 M CAN reflux ,75 min

t

Lett., 1994, 35, 6453

OH Iranpoor.N,; Mothaghineghad, E. Tetrahedron, 1994, 50, 1859

158

Compendium of Organic Synthetic Methods, Vol. 9

Section 124

OMe

&rk.R.M.;

Gac, T.S.; Roof, M.T.S. Tetrahedron Lett., SPDBTO

1994,

35, 8111

SPDBTO 1. Hg(OAc);! , CH2C12 rt , 18h ) Y + +* 2. aq. NaCl 3. Bu$nH, THF

SPDBTO

# n/O

OH

+ x

/O

.

1) 93% Garavelas, A.; Mavropoulos, I.; Perlmutter.P.; Westman, G. Tetrnhedron Lett., 1995, 36,463

(7

v

5% Pd(OAc)2, DMSO ,02 23OC, Id OH

H‘*

*

623

Ronn, M.; BackvaIl, J.-E.; Andersson. P.G, Tetrahedron Lett.,

OH

1995,

BnBr , Cs2CO3, MeCN

OH

92%

OBn

80°C Lee. J.C.; Yuk, J.Y.; Cho, S.H. Synth. Commun.,

90%

,+ H 0 36, 7749

25, 1367

1995,

1. [email protected] 2. (Cp)zTiMez

OiPr 80×80%

3. H2, Pd/C Billington, D.C.; Dorey, G. Synth. Commun., 1995,

SECTION

124: CHO

CsHlJ

ETHERS, EPOXIDES FROM ALDEHYDES

25,

1633

AND THIOETHERS

BuOH , Pd/C , H2 (40 bar), 100°C

also works with ketones Bethmont, V.; Fache, F.; J,eMaire. M, Tetrahedron Lett.,

w

1995,

c8H13 36,4235

,OBu

95%

Section 128

Ethers from Esters

Me&O-

*

PhCHO Et$iH -s.; 4367

159

, TMSOTf

, CHzC12, -3OOC +

O°C

Mori, H.; Kitano, K.; Yamada, H.; Nishizwa.

(t

Ph-Ow

M, Tetrahedron

CH2N2

CHO

A~(OAI-)~ , -78OC , lh

Maruoka, K.; Conception,

Ar = 2,5diphenylphenyl A.B .; Yamamoto. H, Synlett, 1994, 521

ONTs I Ar’sN Me

83%

,NaH,THF

0 H ‘h,, -5OC, Id PhA Baird, C.P.; Taylor. P.C, J. Chem. Sot. Chem. Comnun., 1995, 893 PhCHO

SECTION

125:

126:

ETHERS, EPOXIDES AND THIOETHERS FROM ALKYLS, METHYLENES AND ARYLS

ETHERS, EPOXIDES FROM AMIDES NO ADDITIONAL

SECTION

127:

ETHERS, EPOXIDES FROM AMINES NO ADDITIONAL

SECTION

128:

ETHERS, EPOXIDES FROM ESTERS 1. Dibal , -78OC

Ph’dco2Me

63% (70% ee)

t

NO ADDITIONAL

SECTION

99% L&t., 1994, 35,

2 . TMSOTf

9Py

Kiyooka. S,; Shirouchi, M.; Kaneko, Y. Tetrahedron

EXAMPLES

AND THIOETHERS EXAMPLES

AND THIOETHERS EXAMPLES

AND THIOETHERS OSiMe3 p

Ph T

OMe Lett., 1993, 34, 1491

91%

160

Compendium of Organic Synthetic Methods, Vol. 9

Section 129

1.2SmI2, -3OOC + l-t Ph

2. [email protected],

J

Mobder.

DMAP , TEA CH2C12

G.A; McKie, J.A. J. Am. Chem. Sot.,

115, 5821

PhSH, Pd2(dba)3 , dppb ) THF, Id

mocqMe

Goux, C.; Lhoste,P.; Sinou.D, Tetrahedron,

SECTION

1993,

ETHERS, ETHERS,

129:

1994,

EPOXIDES EPOXIDES

AND THIOETHERS AND THIOETHERS

OBn

a /

ow

2. H30+

Ph

44

S

Ph

0 Satoh.T.: Horiguchi,K. Tetrahedron OMe

Lett., 1995, 36, 4429

1.2.5 t-BuLi , THF -loo”c

t

2. EtCHO Lett., 1995,

-OH

36, 8235

NaBHgN, Bu3SnCl, AIBN 9h

oc

90% 0

* (x

66%

1994,38,2165

1. e’ , Ni (cyclam), DMF , 20°C Mg anode,C fiber cathode

Me,y A

p-Tel.

d?

I

Olivero, S.; CIinet, J.C.; Dufiach,E. Tetrahedron

FROM

OBn

0

Itoh, A.; Hirose,Y.; Kashiwagi,H.; &&&i. Y, Heterocycles,

I

83%

50, 10321

2 BF3*OEt2,CH2C12 / 0ch

mSPh

12H25

Srikrishna.A,; Viswajanani,R. Synlett, 1995, 95

(t

80%

W2H25

62%

Ethers from Ketones

Section 132

161

Phi ,2% Pd(OAc), ,3 NEt3 6% PPh:, , DMF , 70°C

Hillers, S.; J&ger. 0, Synlett, 1995, 153

SECTION

130:

ETHERS, EPOXIDES AND THIOETHERS FROM HALIDES AND SULFONATES

BER-PhSSPh , MeOH, reflux * CsI-I17-S-Ph Yoon. N.M.; Choi, J.; Ahn, J.H. J. Org. Chem., 1994, 59, 3490 c&3

17Br

0I

96%

MeSCHzCl, AlC13 CH2C12 , O°C

/

Olah. G.A.; Wang, Q.; Neyer, G. Synthesis, 1994, 276 PhSH, rt SPh Lee, S.B.; Hong,J.-I, Tetrahedron

tett., 1995, 36, 8439

RelatedMethods:Section123(EthersfromAlcohols).

SECTION

131:

ETHERS, EPOXIDES FROM HYDRIDES

AND THIOETHERS

PIFA = phenyliodine(III)bis(t.rifluoroacetate) Kita. Y,; Takada,T.; Mihara, S.; Tohma,H. Synlett, 1995, 211

SECTION

132:

ETHERS, EPOXIDES FROM KETONES

Tsai. Y-M,; Tang,K-H.; Jiaang,W-T. Tetrahedron

AND THIOETHERS

Lett., 1993, 34, 1303

88%

162

Compendium of Organic Synthetic Methods, Vol. 9

PA,,

TBAF

Capperucci,A.; moceai. A. Tetrahedron

Section 134

A; Ferrara,M.C.; Bonini, B.F.; Mazzanti, G.; Zanti, P.; Ricci,

Lett., 1994, 35, 161 0

/oAc,

Rh2(Ok)4

*

PhF , 10h b

Pirrun~.M.C,; Lee,Y.R. Tetrahedron

0

69%

Lett., 1994, 35, 6231

RelatedMethods:Section124(Epoxidesfrom Aldehydes).

SECTION

133:

ETHERS, EPOXIDES FROM NITRILES

AND THIOETHERS

NO ADDITIONAL EXAMPLES

SECTION

134:

ETHERS, EPOXIDES FROM ALKENES Asymmetric

AND THIOETHERS

Epoxidation

-00

Ph -c

/N-O

, NaOCl +

Mn-salenderivative O°C , pH 11.3

&

58% (77% ee)

Chang,S.; Lee, N.H.; bobsen. m

J. Org. Chem., 1993, 58, 69 39

Mn (salen)catalyst , lh 1%H202, O°C, CH2C12 Schwenkreis, T.; Berkessel,A, Tetrahedron Lett., 1993, 34, 4785

CO2Et

Section 134

Ethers from Alkenes

threitol-strapped iodosylbenzene

Mn-porphyrin

163

, CH$I;!

t

A0

Ph-

, 1,Sdicyclohexylimidazole

86% (69% ee, R+) J.P,; Lee, V.J.; Zhang, X.; Ibers, J.A.; Brauman, J.1 J, Am. Chem. Sot., 1993, 115,

Collman. 3834

l

chloroperoxidase H202

,Bu

, acetone

Bu

9pH 5

—-+v

0

78% (96% e-e, 2R3S) Allain, E.J.; Hager, L.P.; Deng, L.; Jacobsen, E.N. J. Am. Chem. Sot., 1993, 115, 4415 Me02%,, Ph Me02C

I

s

Ph

,B-OMe

0 0

t-BuOOH Manoury, E.; Mouloud,

H.A.H.; Balavoine, G.G.A, Tetrahedron

35% (22% ee , S,S) Asymmetry, 1993, 4, 2339

Mn salen catalyst, 02 PhH,rt

51% (52% ee) T.; Yamada, T.; Nagata, T.; Imagawa, IS. Chem. Lett., 1993,327

Mukaiyama,

-0 Ph )=/ Ph

Ph 32

0 Ph

/N-o

* cat. Mn salen, O°C , buffered bleach , pH 11.3

)7/ Ph

0

69% (93% ee, S,S) Brandes, B.D.; &obss

J. Org. Chem., 1994, 59,4378 cat. Mn(salen) , CH2C12 –

phN

,,yp (42%ee, lS,2S)

Pietikainen.

P, Tetrahedron

Lett., 1994, 35, 941

49%

164

Compendium of Organic Synthetic Methods, Vol. 9

m I/

Section 134

I/ 02

Mn salen catalyst, PhIO , O°C

0

72%(98%ee)

Sasaki,H.; Irie, R.; w.

T, Synlett, 1994, 356 2 PhIO, Mn salencatalyst

ph-

t

Ph

Sasaki,H.;Irie, R.; Hamada,T.; Suzuki,K.; mki. Mn salencatalyst, t-BuCHO PhA

“TPh

rt T, Tetrahedron,

27%(15%ee, lR2R) 1994, 50, 11827

w

02,fl

28% (63:37 cis:trans) 80% eefor cis Nagata,T.; Imagawa,K.; Yamada,T.; Mukaiyama,T. Chem. Lett., 1994, 1259

02, Mn salencomplex, rt NM1 , pivaladehyde, PhF

78%(63%ee) T,; Imagawa,IS.; Nagata,T.; Mukaiyama,T. Bull. Chem. Sot. Jpn., 1994, 67, 2248

B.

Mn (salen)catalyst, Bu4NIO4 imidazole, rt ,3h

Ph

53%(47%ee, lR,ZS (-) )

. . ..*

Pletlkamen.

Tetrahedron

c

I

Lett., 1995, 36, 319

20%4-Ph-pyridineN-oxide, O°C 5%Mn salencomplex, CH2C12

/

Bran&s, B.D.; Jacobsen. E.N, Tetrahedron Lett., 1995, 36,5123

Section 134

Ethers from Alkenes

Ph-

165

8% Mn salen complex , mcpba , NM0

0

*

Ph4l

CH2C12, -78OC

89% (86% ee) Palucki, M.; McCormick, G.J.; Jacobsen. E.N, Tetrahedron

Lett., 1995, 36, 5457

chloroperoxidase , KOAc , Hz02 Ph

antifoamA, aq.acetone,pH 5.2 sodiumcitrate

*

Ph4

1111l111

0

89%(49%ee) Dexter, A.F.; Lakner,F.J.; Campbell,R.A.; Hager.L.P,J. Am. Chem. Sot., 1995, 117, 6412

a3

I

NT.;

02 , Mn salencatalyst, t-BuCHO

/

70%(64%ee) Imagawa,K.; Yamada,T.; Mukaiyama,T. Bull. Chem. Sot. Jpn., 1995, 68, 1455

Non-Asymmetric

Epoxidation

BIPA , FeCl2,02 70°C, Id

mo.

BIPA = N,N’-bis(2-(4-imidazoloyl)ethyl)-2,6-pyridinecarboxamide TJ Moriuchi, T.; Mikami, S.; Ikeda, I.; Ohshiro,Y. Tetrahedron Lett., 1993, 34, 1031 cat. [K-lO-montmorilloniteNi(acac)] 0

iBuCH0 , CH2C12,rt autoclave,10bar Bouhlel,E.; m. P,; Levart, M.; Montaufier, M-T.; Singh,G.P. Tetrahedron Lett., 1993, 34, 1123 -0. P,; Levart, M. Tetrahedron L&t., 1993, 34, 1127

ph*Ph

[CoCl&licylaldehyde-L-serinemethylester] w 02,MeCN,rt,25h

Punniyamurthy,T.; Bhatia,B.; j,qbal.J, Tetrahedron Lett., 1993, 34,4657

‘“TPh 64%

67%

166

Compendium of Organic Synthetic Methods, Vol. 9

h

Fecat.,02,iPrCHO,rt

R.W,; Reihs,S.; Hug, M. Tetrahedron

alfrank.

Section 134

* pgF+ e,

Lett., 1993,

34,

96%

Ph

6033

10%(NH&H4PV6W&4v6 H20 02, DCE,25OC, 4h 2 eq.iPrCH0 77% Hamamoto,M.; Nakayama,K.; Nishiyama,Y.; Ishii. Y, J. Org. Chem., 1993, 58, 6421

P

Co(mac)2,EtCH(OEt)z

C7Hl5

97%

02, MS481.,45OC

mat = 3-methyl-2,4-pentanedibne Mukaiyama,T.; Yorozu, M.; Yakai, T.; Yamada,T. Chem. Lett., 1993, 439

0I msha.

.

CUE,

0

CH3CH0, CH2C12

02,rt, 17h

0

79% S.-I,; Oda,Y.; Naota,T.; Komiya, N. J. Chem. Sot. Chem. Commun., 1993, 139 urea-H202complexfmaleic acid =

BUN

Bu,/f

71%

Astudillo, L.; GaIindo.A,; Gonzalez,A.G.; Mansilla,H. Heterocycles, 1993, 36, 1075 1. [Mn*‘*(TPP)(Cl)], CHs12 I . O-D.;

0 2. imidazole, [email protected],5h

Tangestaninejad, S. Tetrahedron Lett., 1994, 35,945

o= 0

, KHSO5 zc

+

H20KH2C12(pH 11) 18-crown-6,5”C w. .

(9 M,; Ito, S.; Tsutsumi,N.; M&&J,&

Tetrahedron

l

Mt.,

91) 80%

1994, 35, 1577

Section

167

Ethers from Alkenes

AgOAc/bipy/anode ACN (0.1 M LiCLO4) H20

Kandzia,C.; Steckhan. Tetrahedron

-%d

iPrCH0, Fe(AAEMA)3 p02

*

rt, 10h

(-)=, AAEMA =

87%

0

Mt., 1994, 35, 3695

00

Mastrorilli, P.; Nobile, C.F, Tetrahedron

Lett., 1994,

PhzP-‘-PPh, II

35, 4193 0

II

87%

* k=

Ph -LA,&;

0

0

F

Ph H202 Delair, P.; Blass,B.E. Tetrahedron Lett., 1994,35, 8123 S II

1.

EtOlPEt0

SBn

S

2. TBAF.3 H20 wG.;

82%

.

Mecichetti, S.; Neri, S.; Skowr0nska.A. Synlett, 1994, 267 NaOCl ,4-methylpyridine

hJ

P

w

PJ

88%

0

porphyrincatalyst/Mn ; Pereira,M.M.; Serra,AC.; Johns~&pe. R.A.W; Nunes,M.L.P.G. J. Chem. Sot., Perkin Trans. I., 1994, 2053

Y

YO~OZU. K;

Takai,

C7H

15

02 (1 atrn),2% Co(acac)z EtCH(OEt)2,45OC, 1Oh

> 48%

0 T.; Yamada,T.; Mukaiyama,T. Bull. Chem. Sot. Jpn., 1994,67, 2195

Compendium of Organic Synthetic Methods, Vol. 9

168

Section 134

Oxone, 0°C , Bu4NHS04 t

IOBn

acetone , CH-$&

OBn

, buffer 99%

Denmark.S.E,; Forbes,D.C.; Hays,D.S.; DePue,J.S.; Wilde, R.G. J. Org. Chem., 1391 M 0 ‘-x Fg 6

P

1995,

60,

, MeCN, O°C

> 15min Me Yang. DJ Wong, M.-K.; Yip, Y.-C. J. Org. Chem.,

1995,

60, 3887

CO2H I 2 US.;

0-J

hv , methyleneblue PhH , Hz0

/ Thanulingam,T.L.; Rajesh,C.S.; George,M.V. Tetrahedron

Chen,Y.; Beymond.J.-L, Tetrahedron Lett.,

1995,

Lett., 1995,

36, 1337

36,4015

t-B&OH, Ti(OiPr)d, SiO2 w rt, Id Fraile, J.M.; Garcia,J.I.; Mayoral. J,A,; deMhorval,

L.C.; Rachdi,F. J. Chem. Sot. Chem.

Commun., 1995,539

PhIO, NaOCl, Mn salencatalyst t Rasmussen, KG.; Thomsen,D.S.; mn. 2009

w.

92%

K.& J. Chem. Sot., Perkin Trans. l., 1995,

Section 135

Ethers from Misc.

t-B&OH,

169

OH

MeOH

CrS-2- molecular sieve

85%

. Joseph, R.; Sasidharan, M.; Kumar. R… Sud& . A… Ravmdmnathu Commun.,1995,134l

Formation

0

Bosman,C.; DA-ale.

of Other Ethers

PhSeSePh , CAN I

J. Chem. Sot. Chem.

MeOH ,30 min

-c,

A; Resta,S.; Troeolo. C, Tetrahedron

SePh 93% “%, OMe

Lett., 1994, 35, 6525

97%

Marshall. J.A,; Sehon,C.A. J. Org. Chem., 1995, 60, 5966 REVIEW:

“RationalDesignof Manganese-Salen EpoxidationCatalyts;PreliminaryResults,”Hosoya, IV.; Hatayama,A.; Irie, R.; Sasaki,H.; Katsuki.T, Tetrahedron, 1994, 50, 4311

SECTION

135:

ETHERS, EPOXIDES AND THIOETHERS FROM MISCELLANEOUS COMPOUNDS PhSSPh, SbC15,DCE OMe

w

PhS-(=)-OMe

reflux ,3h 76% Mukaiyama, T.; Suzuki, K. Chem. Lett., 1993, 1 LiAlH4, Tic14 PhSOzMe w 93% PhSMe Akgiin, E.; Mahmoud,K.; Mathis. C.% J. Chem. Sot. Chem. Commun., 1994, 761

170

Compendium of Organic Synthetic Methods, Vol. 9

r’u S

[SiO2/SOCl2] 10min

‘rsy

73%

Mohanazadeh. F,; Momeni, A.R.; Ranjbar,Y. Tetrahedron Lett., 0 II

Section 135

1994,

35,6127

CpzTiC12,Sm, THF , rt w

Ph/‘Me Zhann. Y,; Yu, Y.; Bao, W. Synth. Commun., 0 II

Ph”‘ Ph Wang, J.Q.; Zhanrr, Y.M,Synth.

1995,

77-88%

25, 1825

TiC14,Sm, THF , rt ,30 min Commun., 1995,

Ph/‘Me

25, 3545

w

Ph”,

Ph

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

Section 138

CHAPTER

10

PREPARATION SULFONATES

SECTION 136:

171

Halides fkomAlcohols

OF HALIDES

AND

HALIDES AND SULFONATES FROM ALKYNES NO ADDITIONAL EXAMPLES

SECTION 137:

HALIDES AND SULFONATES FROM ACID DERIVATIVES PhIO , NBS , MeCN , 60°C *

Ph-C02H

Ph+Br 73%

Graven, A.; a

SECTION 138:

(96:6 cis:trans)

K& Dahl, S.; Stanczdc,A. J. Org. Chem., 1994, 59, 3543

HALIDES AND SULFONATES FROM ALCOHOLS AND THIOLS

PPh3, (C13COCh0 w PhCH2Cl PhCHzOH Rivero, I.A.; SomanatXlan.; Hellberg, L.H. Synth. Commun., 1993, 23, 7 11

1

95%

BBr~,CH$ld)°Cw < .

Pelletier, J.D.; poiu

Tetrahedron L&t., 1994, 35, 1051

TMSCl , DMSO wh7-4H

&y&

D.C, J. Org. Chem., 1995, 60, 2638

t

c$H 1741

95%

172

Compendiumof Organic Synthetic Methods, Vol. 9

o-

OH

12, pet ether, reflux , 1.5h

Section 142

42%

I

Joseph,R.; Pallan, P.S.; Sudalai, A.; bvindranathm. T, Tetrahedron Left., 1995, 36, 609 Me$iCl , BiC13 OH

rt ,90 min f Labrouihere, M.; Le Roux, C.; Oussaid,A.; Gaspard-Boughmane,H.; Dubu

quant. Bull. Sot.

Chim. Fr., 1995, 132, 522

REVIEWS:

“An Alternative Synthesisof Aryl and Heteroaryl Bromidesfrom Activated Hydroxy Compounds,” IQ&&&y. A.&; Li, J.; Stevens, C.V.; Ager, D.J. Org. Prep. Proceed. int., 1994, 26,439

SECTION 139:

HALIDES AND SULFONATES FROM ALDEHYDES NO ADDITIONAL EXAMPLES

SECTION 140:

HALIDES AND SULFONATES FROM ALKYLS, METHYLENES AND ARYLS

For the conversionR-H + R-Halogen,seeSection 146 (Halides from Hydrides). 2 eq. VO(OEt)CZ2,N2 MeCN , O°C+ rt Ph~si~3

*

PhwC1

6oo/ 0

Fujii, T.; Hirao. T,: Ohshiro. Y, Tetrahedron Lett., 1993, 34, 5601

SECTION 141: HALIDES AND SULFONATES FROM AMIDES NO ADDITIONAL EXAMPLES

SECTION 142: HALIDES AND SULFONATES FROM AMINES 1. TolSO~l 2. base PheNH2

3.NBS,THF,hv

Ph-

Br

86% Collazo. J&; Guziec Jr., F.S.; Hu, W.-X.; Pankayatselvan,R. Tetrahedron Lett., 1994, 35, 7911

Section 146

Halidesfrom Hydrides

173

SECTION 143: HALIDES AND SULFONATES FROM ESTERS NO ADDITIONAL EXAMPLES

SECTION 144:

HALIDES AND SULFONATES FROM ETHERS, EPOXIDES AND THIOETHERS NO ADDITIONAL EXAMPLES

SECTION 145:

HALIDES AND SULFONATES FROM HALIDES AND SULFONATES n-CgH17I, KF , GUI

CICF~02Me

C&I&F3

Cd12, HMPA , 120°C, 8h

Chen. Q-Y,; Duan, J.-X. Tetrahedron Lett., 1993, 34, 4241

SECTION 146:

+ CO2 + MeCl

77%

HALIDES AND SULFONATES FROM HYDRIDES

a-Halogenationsof aldehydes,ketonesand acidsare found in Sections338 (Halide-Aldehyde),369 (Halide-Ketone),359 (Halide-Esters)and 319 (HalideAcids).

BrF3, Br2 , O*C

Br Rozen, S,; Lerman, 0. J. Org. Chem., 1993, 58, 239

t

OMe

BP-(=)-OMe

CH2C12,MeOH 90% Bisawa. SC,; Rao, R. Synth. Commun., 1993, 23, 779

(t

PyH Br3, THF NJ32

–I/

&eves.

W.P,; King II, R.M. Synth. Commun., 1993, 23, 855

87% (19:68 o:p)

Section 147

Compendium of Organic Synthetic Methods, Vol. 9

174

NBS/cat. HZSM-5 OMe

cc4

XeF2, MeCN ,25OC, 6h /

CHO

FQ

CHO

I H Wang, J.; Scott. AJ, Tetrahedron Lett., 1994, 35, 3679

’c’ -/

I H

NH4VO3, H202, KBr 2 phase (H201CHCl3) ,25OC

*

35%

/- r *

50%

Bf

/ 9 9 0

Conte, V.; Di Furia. F,; Moro, S, Tetrahedron Lett., 1994, 35, 7429 I2

I

Qm03)2

I

CH2C12

52%

20°C , 14h

Bachki, A.; Foubelo, F.; Yus, M, Tetrahedron, 1994, SO, 5139

(t (t

HgO-120, CHg12 OBn *

/

&jto.

$=)-OBn

87%

L; Hatakeyama, T.; Takeo, M.; Suginome, H. Synthesis, 1995, 1273 NBS , AcOH , ultrasound, 6h OMe * ..~-(=)-OMe

/

92%

Paul, V.; Sudalai, A.; Daniel, T.; Srinivasan. K,V, Synth. Commun., 1995, 25, 2401

SECTION 147:

HALIDES AND SULFONATES FROM KETONES CF2Br2,Zt-t

IL

F

u. C.-M,; Qing, F.-L.; Shen, C.-X. J. Chem. Sot., Perkin Trans. l., 1993, 335

Section 150

Halides from Misc.

175

SECTION 148: HALIDES AND SULFONATES FROM NITRILES NO ADDITIONAL EXAMPLES

SECTION 149:

HALIDES AND SULFONATES FROM ALKENES

For halocyclopropanations,seeSection 74E (Alkyls from Alkenes). HCl , SiO2 Cl 62% 0 Kn]DD. P.J,; Daus, K.A.; Tubergen, M.W.; Kepler, K.D.; Wilson, V.P.; Craig, S.L.; Baillargeon, M.M.; Breton, G.W. J. Am. Chem. Sot., 1993, 115, 3071

0I

ma.

F

KHF2 , SiF4, rt

79%

M; Shibakami, M.; Kurosawa, S.; Arimura, T.; Sekiya. pb,J. Chem. Sot. Chem.

Commun., 1995, 1891

SECTION 150:

Ph-

N=N-N

HALIDES AND SULFONATES FROM MISCELLANEOUS COMPOUNDS

3

12, CH212,80°C ,4h

w

Ph-I

>98%

Wu, 2.; Jvfoare; J& Tetrahedron Lett., 1994, 35, 5539

m

S

S

Fz,Iz,MeCN,rt +

db ‘

Chambers.;-;

I’

L /

F

I’

52% Atherton, M. .I. Chem. Sot. Chem. Commun., 1995, 177

SOC12,DMF , 100°C 81% C~H25S03Na w325Cl Carlsen, P.H.J.; Rist, 0.; Lund, T.; Helland, I. Acta Chem. Stand. B., 1995, 49, 701

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

176

Section 153

Compendium of Organic Synthetic Methods, Vol. 9

CHAPTER

11

PREPARATION

OF

HYDRIDES

This chapter lists hydrogenolysis and related reactions by which functional groups are replaced by hydrogen: e.g. RCH2X + RCH2-H or R-H.

SECTION

151: HYDRIDES

FROM

ALKYNES

NO ADDITIONAL

SECTION

152: HYDRIDES

FROM

EXAMPLES

ACID DERIVATIVES

This section lists examples of decarboxylations (RC02H + R-H) and related reactions. NO ADDITIONAL

SECTION

153: HYDRIDES

FROM

EXAMPLES

ALCOHOLS

AND THIOLS

This section lists examples of the hydrogenolysis of alcohols and phenols (ROH + R-H). 1. (Bu3Sn)p, To1 , reflux , Id (90%)

QH2hoH

2.2 eq. EtNCO

3. Et$iH , PhH , 140°C 0.05M , benzoyl peroxide (70%) Nishivama. K,; Oba, M.; Ishimi, M.; Sugawara, T.; Ueno, R. Tetrahedron

Ph-OH

1. [PPh3/rf20] , CH2C12 2. NaBH4, rt

3.1NHCl Hendrickson. JB,; Singer, M.; Hussonin, Md.S. J. Org. Chem.,

Wustrow. D.J%;Smith III, W.J.; Wise, L.D. Tetrahedron

* 1993,

ktt.,

1993,

Phn 87% 58, 6913

L&t., 1994, 35, 61

34, 3745

Section 157

Hydrides from Amines

H u;

Cusack, K.P.; Kwochka,

H W.R. Tetrahedron Lett., 1994, 35, 1477

PPh3, Et.$IBr , MeCN

CH3-(CHd9-QH

177

*

e’

C&—W2)g—H

94% Maeda, H.; Maki, T.; Eguchi, K.; Koide, T.; Qhmori. H, Tetrahedron Lett., 1994, 35,4129 CBH17-OH

1. MeCON=C=S

w C8Hl~ 2. Ph$iH , AIBN , 80°C, 10 min

48~83%

Oba, M.; Nishivama, K, Synthesis, 1994, 624 Also via: Section 160 (Halides and Sulfonates).

SECTION

154: HYDRIDES

FROM

ALDEHYDES

For the conversion RCHO + R-Me, etc., see Section 64 (AIkyls from Aldehydes). NO ADDITIONAL

SECTION

155:

HYDRIDES FROM AND ARYLS NO ADDITIONAL

SECTION

156: HYDRIDES

FROM

EXAMPLES

ALKYLS,

METHYLENES

EXAMPLES

AMIDES

NO ADDITIONAL EXAMPLES

SECTION

157: HYDRIDES

FROM

AMINES

This section lists examples of the conversion RNH2 (or R2NH) -+ R-H.

e- , TI-IF/HzO ,60% HNO3 67%

Tpfii. S,; Okumoto, H.; Satoh, H.; Minoshima, T.; Kurozumi, S. SynZett, 1995, 439

178

Compendium of Organic Synthetic Methods, Vol. 9

SECTION

158: HYDRIDES

FROM

Section 158

ESTERS

This section lists examples of the reactions RC02R’ + R-H and RCO2R’ + R’H, HO \

+ UT.;

Pd(acac)z , PBu3 , rt PhH ,3h

.

(alkyne:allene = 99: 1)

CSh7

Matsumoto, T.; Kawada, M.; Tsuii. J, Tetrahedron

$=

J$

SMe

H

*

II other initiators

34, 2161

hv (tungsten lamp) Bu$nH , 0°C

S

l-BflqSi()i

Lett., 1993,

f-l

I

34,

2733

u-o’Ny

were .also used

Barton, D.H.R.; parekh. S&; Tse, C.-L. Tetrahedron

Lett., 1993,

SMe 5 eq. PhSiH3, AIBN

toluene , reflux , lh Barton, D.H.R.; Jang, 0.0.; Jaszverenyi, J.Cs. Tetrahedron,

43

quant.

1993, 49, 2793, 7193

dcoxygenated cyclohexane AIBN , 80°C 99% Gimisis, T.; Ballestri, M.; Ferrer-i, C.; Chatgilaloglu. C,; Boukherroub, R.; Manuel, G. Tetrahedron

Lett., 1995, 36, 3897

Section 160

Ph

4

AC

TBAFex Hz0 , NM0 , THF , rt 1,3-propanedithiol Ph

Ph Ph

w 0

0 Uelo. M4; Okamura, A.; Yamaguchi, J. Tetrahedron

SECTION

179

Hydrides from Halides

HYDRIDES FROM THIOETHERS

159:

99%

Lett., 1995, 36, 7467

ETHERS,

This section lists examples of the reaction R-O-R’ +

Me Hamel. P,; Zajac, N.; Atkinson, J.G.; Girard, Y. Tetrahedron

EPOXIDES

AND

R-H.

Lett., 1993, 34, 2059

5 eq. Ni2B , MeOH-THF t

C 11H23-S-Ph

I

2 NiBr2+

6 NaBH4

__I_)

Ni2B

90%

c 1 lH24

I

Back. T.G,; Baron, D.L.; Yang, K. J. Org. Chem., 1993, 58, 2407

0

DMN* , ascorbic acid , iPr0H hv,3h

SePh &Q&Y.

DMN*

= photoactivated

*

a=’

1,5-dimethoxynaphthalene

85% Cr,; Rao, K.S.S.P.; Sekhar, B.B.V.S. J. Chem. Sot. Chem. Commun., 1993, 1636

SECTION

160:

HYDRIDES

FROM

HALIDES

AND SULFONATES

This section lists the reductions of halides and sulfonates, R-X + R-H.

57% HI, 25OC, 15 min

98%

Wll Wll

Br Penso. M,; Mottadelli,

S.; Albanese, D. Synth. Commun., 1993, 23, 1385

180

Compendium

of Organic Synthetic Methods, Vol. 9

Section 160

Br MeLi,

THF , -105OC

52%

b-

Br

% Grandjean, D.; pale. P, Tetrahedron

L&t., 1993, 34, 1155

M+ B:i,-,:::“;HcHLH OCH2CH2CH2Br

2

an aryl

translocation

24% Lee. EJ Lee, C.; Tae, J.S.; Whang, H.S.; Li, KS. Tetrahedron

2

2

C3H7

61% Lett., 1993, 34, 2343

OH Cl

C

w

w

H

Cl

NaBHz(OCH2CH20Meh

Cl

NiCl2, MeOCHzCHzOH THF ,68OC, 2h

I

Cl Tabaei, S.H.; Pittman Jr.. CU, Tetrahedron

I

/

-4

Lett., 1993, 34, 3263

HC02H , Pd/C , toluene H20, NazCO, , 90°C Cl Cl Barren. J-P,; Baghel, S.S.; McCloskey,

quant. P.J. Synth. Commun., 1993, 23, 1601

PVP-PdC12, H2, 65OC ambient pressure , EtOH , NaOH PVP-PdC12 = palladium anchored on poly(N-vinyl-2pyrrolidinone) Zhang, Y.; Liao. S,; Xu, Y. Tetrahedron Lett., 1994, 35, 4599

0

I

/

quant.

Section 162

cti

181

Hydrides from Ketones

borohydride exchange resin , rt ,3h 0.1 Ni(OAc), , MeOH

17—Bf

Yoon. N.m, Lee, H.J.; Ahn, J.H.; Choi, J. J. Org. Chem.,

.

&I&I.

U,; Sanna, K.D. Tetrahedron

SECTION

161: HYDRIDES

Lett., 1994,

FROM

35,

*

CSH 17-H quant. 59, 4687

1994,

7861

HYDRIDES

NO ADDITIONAL EXAMPLES

SECTION

162: HYDRIDES

FROM

KETONES

This section lists examples of the reaction R2C-(C=O)R Et3SiH , BF3mOEt2, CHg12

+ R2C-H.

*

ph-

Ph mu.

Ph 92%

L Synth. Commun., 1994, 24, 1999

NaBHgN

, BFpOEt2, THF *

rt, 12h

‘(+(=)–c

130–(=)- 94%

Srikrishna. A,; Sattigeri, J.A.; Viswajanani, R.; Yelamaggad, C.V. Synlett,

1995,

93

OzC02Me

OH

1. ClC02Me

A

2, NaBH3

OH

I -OH 94×76%

. ltw. 36,5335

D,; Doecke, C.W.! Hay, L.A.; Koenig, T.M.; Wirth, D.D. Tetrahedron

Lett., 199%

182

Compendium

NHc~Me

of Organic Synthetic Methods, Vol. 9

1. Me$iCl

Section 165

NHCO2Me

, NEt3

2. Et$iH , Tic13 PhAA b Ph &CO,H ma–I Yato, M.; Homma, K.; Jshida. A, Heterocycles, 1995, 41, 17

NaCNBH3, THF BFyOEt;!, rt ,30 min 4

g5%

+

Me0 shna. A,; Viswajanani,

SECTION

.. 2) 85% (3 R.; Sattigeri, J.A.; Yelamaggad, C.V. Tetrahedron

163: HYDRIDES

FROM

SmI2, THF-HMPA

1995,

36,

NITRILES

This section lists examples of the reaction, R-C=N + isonitriles (R-N&). CN

Xem Thêm :   Bà Nà Hill

Xem Thêm :  Mâm quả cưới hỏi gồm những gì cho 3 miền bắc trung nam

tiff.,

R-H (includes reactions of

Ph

, 0°C

CN 97%

CN Ph 3 Hong, W.S.; Cho. Y.S,; Koh, H.Y. Tetrahedron Lett., 1995,

SECTION

164: HYDRIDES

FROM

ALKENES

NO ADDITIONAL

SECTION

165: HYDRIDES

FROM

H 36, 7661

EXAMPLES

MISCELLANEOUS

COMPOUNDS

Mg , EtOH , cat. HgCl2 P

rt

Lee, G.H.; Choi, E.B.; Lee, E.: Pak. C& Tetrahedron

98% Lett., 1993, 34, 4541

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

Section 166

Ketones from Alkynes

CHAPTER

183

12

PREPARATION

OF KETONES

SECTION 166: KETONES FROM ALKYNES

Cha. JS,; Min, S.J.; Kim, J.M.; Kwon, 0.0. Tetrahedron Lett., 1993, 34, 5113

. Tekeuchl.,

78% Yasue, H. J. Org. Chem., 1993, 58, 5386

MeCN , 760°C, 4h OMe CO)sCr

+ Me

(11:l ,33%) Kim, O.K.; 1;vulff. W.D%; Jiang, W.; Ball, R.G. J. Org. Chem., 1993, 58, 5572 0

Ph 1.10% c02(c0)8,

DME

2.20% P(OPh)3 , reflux

Iwasawa, N.; Matsuo, T. Chem. Lett., 1993, 997

0

Compendiumof Organic Synthetic Methods, Vol. 9

Section 167

1. BrzBH*SMez 2. propylene glycol Br

X

Bu

* 3. CH2=CHCH2MgCl, THF , -78OC 4. HMPT , THF , 50°C, HMPA 5. oxidation Brown. H.r; Soundararajan,R. Tetrahedron Lett., 1994, 35,6963

Bu* 95%

MeReO3, H202, tOH Ph

=

Ph

*

Ph

Ph 4f 0

80%

Zhu, 2.; EsPenson.J.ltI, J. Org. Chem., 1995, 60, 7728

SECTION 167: KETONES FROM ACID DERIVATIVES

P

Ph

pAc1 TiCl&Zn ,3% HCl

p)$+;

+p;)=(;

69%

24%

Shi, D.; Chen, J.; Chai, W.; men. W,; Kao, T. Tetrahedron Lett., 1993, 34, 2963 1. (C6h3)2Zn

2. CuCN.2 LiCl

98%

Langer, F.; Waas,J.; -eI. Cl

P, Tetrahedron Lett., 1993, 34, 5261 e’ , [email protected], rt

)

PTPh

80%

meCN 0 0 st. J.-C,; Pereira-Martins, E.; Troupel, M.; Perichon, J. Tetrahedron Lett., 1993, 34, 7571 1. (Me2N=CHCl)Cl, Py MeCN/THF 2 5eq NaN3 O°C * Pa 3:oYG rt ’ Affandi, H.; Bayguen, A.V.; J&&&W, Tetrahedron Lett., 1994, 35, 2729 pt(/co2H

90% N3

185

Ketonesfrom Acids

Section 167

Me0 CgHllCOOH , (PhCO)20, Id 20% (Sic14+ 3 AgC104) CH2C12,rt Me0 T, BUZZ.Chem. Sot. Jpn., 1993, 66, 3729

Kitagawa, H.; m

&Z&&K.;

a

Ph

BU’n*SnBu3 Cl

Ph

Pd(PPh& , dioxane 100°C, 30 h

*

Ph+ 50%

0

Echavarren. A.M,; Perez,M.; CastaiIo, A.M.; Cuerva, J.M. J. Org. Chem., 1994, 59, 4179

0

1. (Ph0)2PON3, NEt3 dioxane , reflux 2.2 M HCl

t

?m

HW 0 w;

61% (2.83 cis:trans) Cowell, J.K.; Harris, L.J. Tetrahedron Lett., 1994, 35, 3883

.

0I 0

t-BuCl/Li/ ultrasound Liofl

, THF

76% Aurell, M.J.; Einhom, C.; Einhom, J.; Luche. J.L. J. Org. Chem., 1995, 60, 8

PhC02Li

iPrC1, Li , THF , ultrasound, rt

*

63% ’ Aurell, M.J.; Danhui, Y.; Einhom, J.; Einhom, C.; Luche, J.L, Synlett, 1995, 459

186

Compendiumof Organic Synthetic Methods, Vol. 9

P

OH

NaI04, MeOH, TEBA

Phx

CO2H Kore, A.R.; Sagar,A.D.; &&&&. 0

92% * DB-18-c6 Ph-L Ph M.m Org. Prep. Proceed. Int., 1995, 27, 373

Ph

* Cl

Han, Y.; Fang, L.; Tao, W.-T.; m.

Cl

0

[PhJGaBuJLi, THF-hexane , 0°C

4f

Cl

Section 168

82%

Ph

Y.-Z4 Tetrahedron Lett., 1995, 36, 1287

Ph

PhMgBr , CuBr , LiBr , THF , 0°C

0

Ph

75%

0

Babudri, F.; Fiandanese,V.; Marchese.G; Punzi, A. Tetrahedron Lett., 1995, 36, 7305

m.

a

EtMgBr , Ni(dppe)Clz 70%

Ph * Cl PhL C,; Aronica, L.A.; Lardicci, L. Tetrahedron Lett., 1995, 36,9185

SECTION 168: KETONES FROM ALCOHOLS AND THIOLS 0.2% his-Ru catalyst, THF 65OC 99% w BackvaIl, J.-E.; Andreasson,U. Tetrahedron Lea., 1993, 34, 5459 1. t-B&OH, H+ *

Ph

2. DBU

80×58% Antonioletti, R.; Arista, L.; Bonadies, F.; Locati, L.; 8cett.t-i.A, Tetrahedron Lett., 1993, 34, 7089 !

1. RuC13.nHz0 , Co(OAch.4 Hz0 2. ;i;k-;,&Ho, 2o”c =c )

Murahashl.. S.-L; Naota, T.; Hirai, N. J. Org. Chem., 1993, 58, 7318

89%

187

Ketonesfrom Alcohols

Section 168

L

H

0.05 Cr03 ,3 eq. 70% t-BuOOH

96%

CH2C12, rt

Ph Muzaft.1; Ajjou, ANA. Synthesis, 1993, 785 0

1. Co(Imd)2 , EtOAc Ph Ph P LH 2. imidazole , CH2C12 0 68% S.-L; Park, D.-C.; Rho, H.-S.; Han, S.-M. Synth. Commun., 1993, 23, 2219

d

OH PDC , Celite , CH2C12

I

25OC, Id

/

55%

Bijoy, P.; Subba Rao. G.S.R,Synth. Commun., 1993, 23, 2701 Cal37

PhI=O ,;(NO&

, DCE

z&l37

OH aldehydescan also be formed quant. Yokoo, T.; Matsumoto, K.; Oshima. K.: UtimoK. Chem. Lett., 1993, 571

(t

V205 , Z1-02, toluene 0

OH llO°C, 6h

-o=

aldehydescan also be formed Nakamura, H.; Matsuhashi, H.; Arata, K. Chem. L&t., 1993, 749

-Q5

88%

5% CoSANSE, MeCN 60070°C, 02, 17h –

-Q+

CoSANSE = ~is(salicylidene-N-(methyl-3-hydroxypropionate))] Co Punniyamurthy, T.; Iabsl. Tetrahedron Lett., 1994, 35, 4007

0

72%

188

Compendium of Organic Synthetic Methods, Vol. 9

Phi ,3% Pd(OAc)2, DMF

Section 168

Ph+O

w

3 eq. KOAc , 80°C, 3d

40%

Larock. RC,; Yum, E.K.; Yang, H. Tetrahedron, 1994, 50, 305

9 02

OH

(t

0

79%

CoSANSE * o= CoSANSE = chiral cobalt catalyst IQ&a, S.J.S.; Punniyamurthy, T.; Iqbal. J, Tetrahedron Lett., 1994, 35,4847

9 J+ z

t-B&OH, EhNOH , rt [OsO4] , aq. t-BuOH ,

fi

HO

i k

1 OH Beck, C.; Seifert. & Tetrahedron Lett., 1994, 35, 7221 0.5% Ru complex ,20% Co complex 0.5 02 , toluene , 1OOOC,36h 87% 2,5-dit-butyl-1,4-benzoquinone

0 OH Wang, G.-Z.; Andreasson,U.; Backvall. J.-E, J. Chem. Sot. Chem. Commun., 1994, 1037 cat. PdC12, cat. Adogen 464 9.3h, Nag03 , DCE , reflux

A&Mohand,

t-B.=-(-}=O

also for primary alcohol + aldehydes S.; Henin, F.; Muz . J, Tetrahedron Lett., 1995, 36, 2473

“;;;;t”,;OAc

)

t-B+(-)=0 96%

Murahashi. S-I,; Naota, T.; Oda, Y.; Hirai, N. Synlett, 1995, 733

189

Ketonesfrom Aldehydes

Section 169

OH Co(acac)3,02, MeCN ,75’C

93% O Iwahama, T.; Sakaguchi,S.; Nishiyama, Y.; Ishii. Y, Tetrahedron Lett., 1995, 36, 6923

6D

Bacillus stearothemophilus

‘4 %

heptane

*

64

0 49% 100%ee (lS,SR) Fantin, G.; Fogagnolo, M.; Giovannini, P.P.; Medici. A; Pedrini, P.; Poli, S. Tetrahedron Lett., 1995, 36, 441 OH

‘OH

0

cat. CoC12(PPh& , t-BuOOH /

93%

DCE , heat, 4.5h

Ph

aldehydescan also be formed Dyer. &; Varghese, J.P. Synth. Commun., 1995, 25, 2261 H

L

e’ , RuO2, aq. MeCN , Bu,$JOH

89%

Bu$JBr Ph Torii, S.; Yoshida, A. Chem. Lett., 1995, 369 RelatedMethods: Section48 (Aldehydesfrom Alcohols and Phenols).

SECTION 169: KETONES FROM ALDEHYDES

0.05 Rh(R-BINAP)ClOd CH2C12,rt ,30 min

(3

97) 81% (>99%ee3S,4S)

Wu, X.-M.; Funakoshi, K.; Sakai. K, Tetrahedron Lett., 1993, 34, 5927

190

Compendium of Organic Synthetic Methods, Vol. 9

Section 169

71% Punniyamurthy, T.; Kalra, S.J.S.; Qbal. J, Tetrahedron Lett., 1994, 35, 2959

PhCHO

1. t-BuMe$iCBrzLi 2. set-BuLi

, -78OC + rt

3. PhCHO 4. HMPA Shinokubo, H.; Oshima. K.: IJtimotu

0

*

PhkPh

5g%

Tetrahedron Lett., 1994, 35, 3741

59% (78% ee , S) Barnhart, R.W.; Wang, X.; Noheda, P.; Bergens, S.H.; Whelan, J.; Bosnich.B,. Am. Chem. sot., 1994, 116, 1821 Me$iCBr3

PhCHO

, CrBq/LiAlHq

THF , 60°C

mn.

D.M.; Comma, P.J. Synlett, 1994, 663

PhCHO CH(OEt)3, H+ , THF

Katritzkv.

2. BuLi, THF , -78OC 94% 3. EtBr 4. H+ A.R,; Lang, H.; Wang, 2.; Zhang, 2.; Song, H. J. Org. Chem., 1995, 60, 7619 C&I $xCpCl

,20% ZnBr2

PhCHO

*

PhCHO *

THF ,3h ,25OC Zheng, B.; Sreb&

M, J. Org. Chem., 1995, 60, 3278

Section 171

Ketones from Amides

SECTION 170:

191

KETONES FROM ALKYLS, METHYLENES AND ARYLS

This section lists examples of the reaction, R-CH2-R’ -3 R(C=O)-R’. 5% CoSANSE , MeCN Ph-

t

Ph

cat. 2-oxocyclopentene carboxylate 60°C, 15h, O2 CoSANSE = ~is(salicylidene-N-(methyl-3-hydroxypropionate))] Co Punniyamurthy, T.; IabaI. J, Tetrahedron Lett., 1994, 35, 4003

t’h

69%

OMe OMe

[email protected], Me$YBF3 CH2C12, -78OC+ rt 76%

Kiselyov, A.S.; m.

R.G, Tetrahedron Lett., 1995, 36, 4005

SECTION 171: KETONES FROM AMIDES

Me

N I OMe

OMe I N Me

0 1.2 eq. PhLi Ph +

2 . H+

Ph 4f

0

75% O

Sibi. M.P,; Marvin, M.; Sharma, R. J. Org. Chem., 1995, 60, 5016 1.2.2 BuLi , -78OC cN-(

,Ph

t 2. AcOH 3. K,C03,65°C

,.ji

ph

82% Brandange, S.; Holmgren, E.; Leijonmarck, H.; Rodriguez, B. Actu Chem. &and. B., 1995, 49, 922

G

N-

1.2 eq. PhLi t

C02Et 2. H30+

Ph Prakash, G.K.S.; York, C.; Liao, Q.; Kotian, K.; Qlah. G.A, Heterocycles, 1995, 40, 79

95%

192

Compendiumof Organic Synthetic Methods, Vol. 9

Section 172

2 eq. EtAIC12, rt , 12h Ph Ph7

N I

56%

Ph

CH2Q

so2

Iwama, T. Tetrahedron Lett., 1995, 36, 245

-T.;

0

PhMgBr

PhK

68% Ph

. Kashlma. CJ Kita, I.; Takahashi, IS.; Hosomi, A. J. Heterocyclic Chem., 1995, 32, 25 REVIEW:

“Chemistry of N-Methoxy N-Methyl Amides. Applications in Synthesis.A Review,” S M.P. Org. Prep. Proceed. Int., 1993, 25, 5

SECTION 172: KETONES FROM AMINES 1. “X” 2. H30+

t

3 = H

40% X = octane,230°C ,2h X = t-BuOK./BuLi/THF/-50°C ,2h 73% Sprules, T.J.; Galpin, J.D.; Macdonald, D, Tetrahedron Lett., 1993, 34, 247

[email protected]

9 W04 9ether 25OC, lh

Harris, C.E.; Lee, L.Y.; Dorr, H.; Singaram. B, Tetrahedron Lett., 1995, 36, 2921

75%

Section 174

Ketonesfrom Ethers

193

/OH o= % )=c

7% 86% Gao, J.; Hu, M-Y.; Chen, J-x.; Yuan, S.; Chen, W-x Tetrahedron L&t., 1993, 34, 1617

86%

Pa

Lett., 1993, 34, 3951

Section 177

Ketonesfrom Ketones

d

Tick, CH&

199

92%

lIllIIIIIISi(i~)3

-78OC + -2OOC

& Kniilker. H.-J; Graf, R. Tetrahedron Let?., 1993, 34,4765

(5: 1 anti:syn)

98~72%

pandey. G,; Krishna, A.; Girija, K.; Karthikeyan, M. Tetrahedron Let?., 1993, 34,663l 1. LiN(TMS)z A/q/

:-.:;:,.,

,4h

+ + 95%

Reetz.;

Haning, H. Tetrahedron Let?., 1993, 34, 7395

Cossy. J,; Furet, N. Tetrahedron Let?., 1993, 34, 8107

0

kEi:%ir?-t, 18h ) &J~.I+ 56~~~lohexmo

J&&s. R&; Taylor, S.R. .I. Org. Chem., 1993, 58, 4469

Cahlez. G,; Figadbe, B.; Cl&y, P. Tetrahedron Let?., 1994, 35, 3065

Section 177

Compendiumof Organic Synthetic Methods, Vol. 9

200

,,,,\I”’

TMS

4

CF$&Ag

, Me1 -CH2C12,-78OC+ rt

+

4

..

(6 1 P, Tetrahedron Lett., 1994; 35, 367

Angers, P.; we.

rc 1)

Chen, L.; Gill, G.B.; Pattenden.G, Tetrahedron Lett., 1994, 35, 2593 1. MeLi 2. MnC12 Ph

3. PhCH2Br ; Chau, K.; Cl&y, P. Tetrahedron Lett., 1994, 35, 3069 0 0

BuA

MeCHN2 , Me3Al ,O”C CH2C12, lh

Bu

Maruoka, K.; Conception, A.B.; -to.

/I & #

*

55%

Me I& J. Org. Chem., 1994, 59,4725

2.5 eq. BuySnH , AIBN *

Cl

0T

Bu Bu K,

8h slow addition

q 0 Dowd. PJ Zhang, W.; Mahmood, K. Tetrahedron Lett., 1994, 35, 5563

57%

0

78%

201

Ketonesfrom Ketones

Section 177

SC-1 , Ni2B , H2 (1 atm) 0

*o=O

+

Q-OH

(>99

: B, Tetrahedron Lett., 1994, 35, 5595

BeIisle, C.M.; Young, Y.M.; S

SiMe3

Ph

Ph

Ph

1) >99%

Ph

0

Yb,THF,40°C,2h

CHPh;!

‘r(

Ph

Ph

+

OH 68% 29% Taninuchi. Y,; Nagafuji, A.; Makioka, Y.; Takaki. K.: Fujiwara. Y, Tetrahedron Lett., 1994, 35, 6897 0

&

hv’NEt3

t

0

&

48%

Kirschberg, T.; [email protected] J, Tetrahedron Lett., 1994, 35, 7217 Ph Rh2(O$R*)4, CHgl2, -2OOC,2h 0 Ph

N2

64%

(77% ee , S) Watanabe,N.; Ohtake, Y.; &phimoto. S,; Shiro, M.; Ikegami, S. Tetrahedron L&t., 1995, 36, 1491

Ph

Ph

CHO

Ph *

S 2277

Ph

84%

cat. TMSOTf , rt , CH#2,5h 0 SE; Awachat, M.M.; Kelkar, S.V. Tetrahedron L&t., 1995, 36,

Section 179

Compendium of Organic Synthetic Methods, Vol. 9

202

0

C&12, SmI2, TI-F ,5h

61% -s.;

Tsuchimoto, T. Tetrahedron Lett., 1995, 36, 5937 Bu$nCl – NaBH3CN, AIBN SO;?Ph

t-BuOH , heat

86% Giovannini, R.; Petrini. M,Synlett, 1995, 973 REVIEW: “Organotin Enolates in Organic Synthesis. A Review,” Shibata. I,; Baba, A. Org. Prep. Proceed. Int., 1994, 26, 123 Related Methods: Section 49 (Aldehydes from Aldehydes).

SECTION 178: KETONES FROM NITRILES NO ADDITIONAL

EXAMPLES

SECTION 179: KETONES FROM ALKENES

k

1,4-dimethoxybenzene(sensitizer) hv , MeCN , 12h, rt

Ph B.

0 –

> Ph

90% conversion b-p-d

IJ.T,; Sridhar, M. Tetrahedron Lett., 1993, 34,434l

I + (x S

GTign.;

I

TlOAc , CO, MeCN 80°C, 16h 10% [Pd(OAch/2 PPh3]

I L s

75% Khalil, H.; Levett, P.; Virica, J.; Sridharan, V. Tetrahedron Lett., 1994, 3.5, 3197

Section 179

Ketones from Alkenes

203

10% Pd(OAc), ,20% PPh3 Et4NC1 , CO

88% Gring.;

Redpath, J.; Sridharan, V.; Wilson, D. Tetrahedron L&t., 1994, 35, 4429 1. Et2BHaSMe2 , ether, 25OC 2. Et$n , neat, O°C

Ph 3. CuCN.2 LiCl , THF , O°C 4. PhCOCl d Langer, F.; Devasagayaraj, A.; Chavant, P.-Y.; mochel. P, Synlett, 1994, 410

84%

Me3SiN3, CH2C12,CrQ 59% Reddy, M.V.R.; Kumareswaran, R.; m.

Y.D. Tetrahedron L&t., 1995, 36, 6751

1. [CK12*THF/PhEt2N:BH3, ClOH2w/

PhH , CO]

: ;5:r36h . 9 4. H202, NaOH , NaOt-Bu

C~H2JLH. 70%

Rao, M.L.N.; Periasamv. M, Tetrahedron Lett., 1995, 36, 9069

0 A

9 w=ma *

2 PPh3, DCE d (>20 Lautens. MJ Edwards, L.G.; Tam, W.; Lough, A.J. J. Am. Chem. &..

d 1) 99% 1995, 117, 10276

204

Compendium of Organic Synthetic Methods, Vol. 9

Section 180

1. Cl$=C=O 2. Bu$nH , AIBN 85% (84:16) Dowd. P,; Zhang, W.; Geib, S.J. Tetrahedron, 1995, 51, 3435 See also:

Section 134 (Ethers from Alkenes). Section 174 (Ketones from Ethers).

SECTION 180:

KETONES FROM MISCELLANEOUS COMPOUNDS

Conjugate reductions and reductive alkylations of enones are listed in Section 74 (Alkyls from AIkenes). Ph

>

5) 0

9m

Ph

9 C&Cl2

0 20°C , 30 min 92%

TFP= l,l,l-trifluoropropane Ahamura, A.; Curci, R,; Edwards, J.O. .I. Org. Chem., 1993, 58, 7289

#-(-)=NoH ooc,loi?~ * -(-)=o acetone ,

80% Olah. G.A,; Liao, Q.; Lee, C.-S.; Prakash, GKSJynlett, Ph

O3 , CH2C12, -2OC ,2h

1993, 427

Ph

N-OH * > Ph Yang. Y.; Li, T.; Li, Y. Synth. Commun., 1993, 23, 1121 N—NHTs

PhI(OA&

> Ph

0

95%

, MeCN , rt , 10 min w

Ph

Ph Me

Me 87% Zeng, H.; Chen. Z-C, Sytih. Commun., 1993, 23, 2497

Section 180

J

Ketonesfrom Misc.

205

TS-1, H202, MeOH, 4h

-NHTS

84%

TS-1 = titanium silicate molecular sieves Kumar, P.; Hegde, V.R.; Pandey,B.; Ravindranathan. T, J. Chem. Sot. Chem. Commun., 1993, 1553 Ph

Ph

KMn04, aq. MeCN , rt , lh N-OH

0 *

95%

k=

Wali, A.; Ganeshpure,P.A.; Satish. S&11. Chem. Sot. Jpn., 1993, 66, 1847 NO2

NflHdH202

K2CO3, MeOH Ballini. R,; Bosica, G. Synthesis, 1994, 723 NNHcoNH2

hJ-

PhI(OAc);?, aq. MeCN

0 w

80%

P Me Chen, D.W.; Chen, ZC, Synthesis, 1994, 777

N-NMe2

Me

@uqN)2Sz& 7DCE reflux , lh

Choi, H.C.; m.

&Synth.

N-OH P +

Commun., 1994, 24, 2307

Bentoni te/AgzC03 , PhH

0 t

50%

Ph *

reflux ,4h Me Me Sanabria, R.; Miranda. R,; Lara, V.; Delgado, F. Synth. Commun., 1994, 24, 2805

d=

N-NHTs

(Bu4N)2S208, DCE , reflux 0

lh =c

95%

0

Chen F,; Yang, J.; Zhang, H.; Guan, C.; Wan, J. Synth. Commun., 1995, 25, 3163 REVIEW:

“Macrocycle Synthesis:Cyclic Ketones,Ketoalkenes,Diketones and Dienes of Ring Size C21 Dang, Y. Org. Prep. Proceed. In?., 1993, 25, 309 to &jr” EQ-;

Section 180A

Compendium of Organic Synthetic Methods, Vol. 9

206

SECTION

180A: PROTECTION

OF KETONES

[Rh(MeCN)3(~phos)l Wfh

I7

acetone, rt ,4h

*

PhJL

90%

Me

/ 9 * 00 o= .M, Tetrahedron Lett., 1993, 34, 8071 HS

SH

n ,-c

S

3m12

0

rt

S

92%

m

Y J Yu, Y.; Lin, R. Org. Prep. Proceed. Int., 1993, 25, 365

p-TsOH , PhH , reflux , cat. TMSI

9

DDQ 9H20 C&C12 95% McDon;tld. CL; Nice, L.E.; Kennedy, K.E. Tetrahedron Lett., 1994, 35, 57 MesSid/

0

SiMq OS iMe

CF$O$iMe3 , CH2C12 -78OC

o=

(–bti3

4

LiBF4, MeCN , heat 96% Lillie, B.M.; Avery, M.A. Tetrahedron Lett., 1994, 35, 969 AcCl ,2% SmC13 , rt * 15 min Wu. S.-H.; Ding, Z.B. Synth. Commun., 1994, 24, 2173

Section BOA

Protection of Ketones

207

cat. Pd(OAc)z ,2 NaOAc ,02 )

OSiMe3

58%

0

DMSO

o= Larock. R.c, Hightower, T.R.; Kraus, GA.; Hahn, I?; Zheng, D Tetrahedron Lett., 1995, 36, 2423

S

S

Se02 , AcOH , rt ,25 min

0 .

98%

aldehydes can also be used Phx outounian. S.A, Synthesis, 1995, 39

CuSO4/SiO2, CHC13 20°C ,2d

Caballero, GM.; Gras. E.G,Synth. Commun., 1995, 25, 395

Kurihara, M.; Miyata, N. Chem. L&t., 1995, 263

See Section 362 (Ester-Alkene) for the formation of enol esters and Section 367 (Ether-Alkenes) for the formation of enol ethers. Many of the methods in Section 6OA (Protection of Aldehydes) are also applicable to ketones.

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

208

Compendium

CHAPTER

13

PREPARATION

SECTION

OF

181: NITRILES

FROM

NITRILES

ALKYNES

NO ADDITIONAL

SECTION

182: NITRILES

FROM

183: NITRILES H

A

W-h

FROM

MezC(CN)OH

EXAMPLES

ACID DERIVATIVES

NO ADDITIONAL

SECTION

EXAMPLES

ALCOHOLS

AND THIOLS CN

, MeCN , DEAD

58%

/ C6Hl

Me

. ilk. EL& Synth. Commun.,1993, 23, 2481

SECTION

184: NITRILES

FROM

WCHO

MeOH, rt

* 2. “crude” , MeOH , O°C 2.4 MMPP6 Hz0

aCN 88%

MMPP = magnesium monoperoxyphthalate R.; Gasch, C.; Lassafwm J-K; Llera, J-M.; Wzquez, TetrahedronLett., 1993,34, 141

Ferbdez,

185:

NITRILES ARYLS

Me

ALDEHYDES

1. Me$WI-I2,

SECTION

Section 185

of Organic Synthetic Methods, Vol. 9

FROM

NO ADDITIONAL

ALKYLS, EXAMPLES

J.

METHYLENES

AND

Section 190

SECTION

Nitriles from Halides

186: NITRILES

FROM

AMIDES

Ph

2 PPh3, 2 cc14 Ph

e

209

97% CN H other reagents are also given that lead to this conversion Waers. M.A.; Hoem, A.B.; Arcand, H.R.; Hegeman, A.D.; McDonough, C.S. Tetrahedron Lett., 1993,34, 1453 0

PhA

*

3 NEt3

Ag20, Et1, PhH,25OC

Sznaidman,M.L.; Crasto,C.; Hecht, SM. Tetrahedron

/I(

NH2

0

Correia.J, Synthesis,

SECTION

Ph-CN

(dark), MS 4A, 12h

NH2

Bu

y-

1994,

Lett., 1993,34, 1581

NaOCl, NaBr, PhWH20 w TBAHS04, [email protected] 1127

187: NITRILES

FROM

82%

Bu-C-N

=

55%

AMINES

NO ADDITIONAL EXAMPLES

SECTION

188: NITRILES

ph-OAc

FROM

ESTERS

Me$iCN,

WPPh& *

THF , reflux ,16h

PhMCN 98% (E.-Z, >9:1)

Tsuji. Y,; Yamada,N.; Tanaka,S. J. Org. Chem., 1993, 58, 16

SECTION

189:

NITRILES FROM THIOETHERS

ETHERS,

EPOXIDES

AND

NO ADDITIONAL EXAMPLES

SECTION

190: NITRILES

I

FROM

HALIDES

AND SULFONATES

1. BuLi, THF, -1OOOC 2.ZnI2 , -loo”c + o”c 3. TosCN, -78OC+ rt ,3h

CN –

Klement,I.; Lennick,K.; Tucker,C.E.; Knochel,P, Tetrahedron

0

84%

Lett., 1993, 34,4623

210

Compendium of Organic Synthetic Methods, Vol. 9

MezC(CN)OH , MeCN , TMG *

MBr

MCN

TMG= 1,1,3,3-tetramethylguanidine Dowd. P,; Wilk, B.K.; Wlostowski, M. Synth. Commun., 1993, 23, 2323 TiC4,

9-

PhgH-CN 93%

Ziener. HE,; Wo, S. .I. Org. Chem., 1994, 59, 3838

191: NITRILES

FROM

HYDRIDES

NO ADDITIONAL

SECTION

192: NITRILES

71%

TMSCN , CH2C12 , O°C

PhgHCl

SECTION

Section 194

FROM

EXAMPLES

KETONES

1. secBuLi, TMSCl 2. secBuLi1

CN

0

ck= t-Bu

89%

3. Me1 4. NaOMe

alsoworkswith aldehydesubstrates Santiago,B.; u.

A.& Tetrahedron

A 0

Ph

Lett., 1993, 34, 5839

1.Me(Cl)AlNH;! * CF3

Kende.AS,; Liu, K. Tetrahedron Lett., 1995, 36, 4035

SECTION

193: NITRILES

FROM

NITRILES

Conjugatereductionsand Michael alkylations of alkene nitriles are foundin Section74D (Alkyls from Alkenes). NO ADDITIONAL

SECTION

194: NITRILES

Ph—-CN

2. t-BuOK

FROM

EXAMPLES

ALKENES

NO ADDITIONAL

EXAMPLES

85%

Section 195

SECTION

Nitriles from Misc.

195:

NITRILES FROM COMPOUNDS

211

MISCELLANEOUS

83%

Dandgar.B.P%;Jagtap,S.R.; Ghodeshwar, S.B.; Wadgaonkar,P.P.Synth.Common., 1995,25, 2993

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

212

Compendium of Organic Synthetic Methods, Vol. 9

CHAPTER

14

PREPARATION

SECTION

Section 196

196: ALKENES

OF

FROM

Ph-C=r-Ph

ALKENES

ALKYNES

, DMF , 120°C

10%Pd(OAc)z,20% PPh3 2 TlOAc ,36h Griw Q, Kennewell,P.; Teasdale,A.; Sridharan,V. Tetrahedron Let?., 1993, 34, 153

xz OTs

w;

.

(PhMe$i)$uCNLi2 THF , -78OC -3 rt

de Marigorta,E.M. Tetrahedron Let?., 1993, 34, 1201 1. *&

C3H-W7

vrt

C3H7

$7

Cp2Zr(CH2=CH2). Id

* -c, 68% 2. H+ . Takahashl,T,; Kondakov,D.Y.; Suzuki,N. Tetrahedron Let?., 1993, 34, 6571

(Me$i)$iH , hv (sunlamp) 2h, hexane 70%

Pattenden.G,; Schulz,D.J. Tetrahedron

Let?., 1993, 34, 6787

Section 196

Alkenes from Alkynes

I

NO2

+

0

I

10% Pd(OAc)z 20% PPh3 , DMF TI(OAc) , 130°C 18h

I b Et&C

‘C02Et Sridharan, V. Tetrahedron

Brown, S.; Clarkson, S.; Grign.;

Le ‘tt., 1993,

34,

157

1.Cp$r(H)Cl , CHg12 20°C ,20 min w 2.5% AgC14

10min TBDMSO Wiof. P,; Xu, W. .I. Org. Chem., 1993, Ph

/-

0 0 58,

825

TBDMSd

92%

/

1. t-BuLi , pentane/ether 2. -78OC + rt + -78OC )

I

0

99% z) Lett., 1994,

J.-F, Tetrahedron

hv , 1%CpCo(CO)2, PhH, heat

Stammler,R.; Malacria. SiMe3

35, 6677

-Bu-Bu

Brasseur,D.; Jestin,J.-L.; Nom

C02Me

1994,

23) 69% 54% de

1. [email protected] , ether 2.2 eq. BuLi , -4OOC , Me2S 3. NH3/NH&l

/ Ph

35, 4669

35,

C02Me

b

93%

W Synlett, 1994, 92

1. Cp$rBu2, PMe3 2.35”C , Eto 9

5c Me$i3OEt

Et0

71%(53:47 cis:trans) 3. H30+ . Takahashl.; Kondakov,D.Y.; Suzuki, N. Chem. Lett., 1994,259 Ph

E

NiBr;?-Zn, diphos, H2

* phm g2% sakai. &; Takai, Y.; Mochizuki, H.; Sasaki,K.; Sakakibara,Y. Bull. Chem. Sot. Jpn., 1994, 67, 1984

Compendium of Organic Synthetic Methods, Vol. 9

216

Section 197

QSiEt3

OSiEt3 3% (PCy3)g12Ru=CHCH=CPh2 CHzC12, (0.6 M) ,2X

,8h

P tie Me Kim, S.-H.; Bowden,N.; mbbs. RcfL J. Am. Chem. Sot., 1994, I16, 10801 Me$iI , Me$n , dioxane SiMe3

95%

61%

5% Pd(PPh3)4,25OC,8 h Chatani,N.; Amishiro,N.; Morii, T.; Yamashita,T.; Murd. S,J. Org. Chem., 1995, 60, 1834 OSi(OEt)3 OH-

Me20%CpZTi(PMe&, HSi(OEt)3

-)&

Me 73%

Qowe. WL; Rachita,M.J. J. Am. Chem. Sot., 1995, I1 7, 6787 Br SmI2,THF , DMPU P2

Phd

= 83%

Zhou,2.; Larouche,D.; Bennett.

SECTION

197: ALKENES

Tetrahedron,

FROM

1995, 51, 11623

ACID DERIVATIVES

0.01PdC12(PPh&, PPh3 c6H’-C0

2H

P 250°C, N2

c6H1v

Miller. J.A,; Nelson,J.A.; Byrne, M.P. J. Org. Chem., 1993, 58, 18 M Cl

, Me$i-SiMe3 , toluene

5%Pd(dba)z, 80°C,4h

Obora,Y.; Tsuii. Y,; Kawamura,T. J. Am. Chem. Sot., 1995, 117, 9814

9840

section 199

SECTION

Alkenes from Aldehydes

198: ALKENES OH

FROM

217

ALCOHOLS

AND THIOLS

H-montmorillonite

dioxane c9H19~ + C9H19d (air free) . reflux ,6h 19) 91% (81 Santhi, P.L.; Siddiqui, M.F. Tetrahedron L&t., 19b3, 34, 1185 –

Kantam. OH

OH

1. SOCl;!, NEt3, 0°C rt NMe(OMe) 2.DBU,0°C + ~

Ph

NMe(OMe)

Ph

92%

T ee) (96.98% Bennani,Y.L.; m.

K.B. Tetrahedron Lett., 1993, 34, 2083 Mo(acac)s, dioxane, reflux

c lOH23

C10H23

OH -f

* (1

+ c1a2Y . 1) 92%

Prasad,A.D.; Santhi,P.L. Synth. Commun., 1993, 23, 4;

Kantam.;

phflp::::::’ wph-/c+ ,,/orr

Dorta, R.L.; SE.;

SECTION

73%

8%

Betancor,C. Tetrahedron Lett., 1994, 35, 5035

199: ALKENES

FROM

ALDEHYDES

Me 1.2 LDA Et0 2. PhCHO (>98:2 , E:z)

Coutrot.Ph,; Grison,C.; Gkardin-Charbonnier, C.; Lecouvery,M. Tetrahedron 2767

Lett., 1993, 34,

Compendium of Organic Synthetic Methods, Vol. 9

Section 199

MezCHzPPh3+ BrBuLi , THF , -78OC Ph

SiMes-Bu [94:6 E.-Z (>98%ee, R)]

Bhushan,V.; Lohray, B.B.; En&.

D, Tetrahedron Lett., 1993, 34, 5067

1. H2S, THF , -3OOC 2. NH2NI12 3. -3OOC ,4h C7Hl

seCHO

co1kizo, L .R.; Q&c

a

AC

4. MgS04, -3OOC 5. CaCO3, Pb(OAc)d -c7H-IliI 6. THF , reflux 7. PPh3, THF , reflux Jr.. F& J. Org. Chem., 1993, 58, 43 Cfl l~H0,Zr-t , CrCl3, DMFm

Br

56%(91:9E:Z)

Knecht, M.; Boland.W,Synlett,

1993, 837

CN

CH2(CN)2, CdI2,neat PhCHO heaat,5 min

*

95%

A Ph

CN Prajapati,D.; Sandhu.JS, J. Chem. Sot., Perkin Trans. l., 1993, 739 Bu+CH 2Br2 , 25°C Li , CrCl2, DMFII’HF

Me020CH0

‘,

Me02C///n/SnBu3 61%

w

D.M; Boulton,L.T.; Maw, G.N. Tetrahedron Lett., 1994, 35, 2231 wCH0

[PPh3=CHMe/I$2NaNTMS23 = *42% (1O:l Z:E)

Chen,J.; Wang,T.; aao. K, Tetrahedron

Lett., 1994, 35, 2827

SiMe3

(Me$i)2CBr2, CrC12 PhCHO &&on.

) DMF ,25”C

D.M,; Comina,P.J. Tetrahedron

84% Ph

Lett., 2994, 35, 9469

SiMe3

Section 200

AIkenes from Alkyls

E10*~-Lpp~3+ Cd-J

219

Br- , dioxane

QH13

13CHO

Ph& , hv , K2CO3, H20, 90°C, 2h

YCOEt

70% (78:22 E:Z)

2

(withouthv 12:18 E.-Z) Matikainen,J.K.; Kaltia, S.; Hase.T,SynZett,1994, 817 EtOzC/sMe3

PhCHO,

DMSO t

EtO&-WPh

cat.CsF, rt + 100°C aed.

93%

M; Ozanne,N. J. Org. Chem., 1995, 60, 6582

SiMe3 PhCHO

t

80%

25OC Ph’+ N-4; Staszewski,J.P.; Fuk, D.-K. Tetrahedron Lett., 1995, 36, 3619

c

C02Et 1. KHMDS , THF, lh 5 eq. lg-crown-5,-78OC 0 w / P 2. PhCHO I Ph PhO OPh Ic Tetrahedron

+ 4 Ph

..

(99 A&I.

EtOg

C02Et

1) 98%

Lett., 1995, 36,4107

C02H

Me3SiCH=C=O,BF3GEt2 PJCHO mk.

-/P

90% (1:l E.-z) T&; Zhang,Y.; Huang,J.; Smith, D.C.; Yates,B.E. Synth. Common., 1995, 25, 15 RelatedMethods:Section207(Alkenesfrom Ketones).

SECTION

ZOO:

ALKENES FROM AND ARYLS

ALKYLS,

METHYLENES

Thissectioncontainsdehydrogenations to formalkenesandunsaturated ketones,estersand amides.It alsoincludestheconversionof aromaticringsto alkenes.Reductionof arylsto dienesis foundin Section377(AIkene-Alkene).Hydrogenation of arylsto a.Ikanes and dehydrogenations to formarylsareincludedin Section74 (Alkyls from Alkenes).

220

Compendium

of Organic Synthetic Methods, Vol. 9

Section 203

CgK , THF

*

Weitz, 1.S.; wov&.

M1 J. Chem. Sot., Perkin Trans. I ., 2993, 117 Br Me0

A

2F

Pseudomonas cepacia AC1 100

OHC

OH

* OMe Artaud, I.; Tomasi, I.; Martin, G.; Petre, D.; Mansuy, D. Tetrahedron

SECTION

201: ALKENES

Related Methods:

FROM

ti:H CHO Lett., 1995, 36, 869

AMIDES

Section 65 (Alkyls from Alkyls). Section 74 (Alkyls from Alkenes). 1. PhLi, THF , 0°C 85%

Jurata, H.; Ekinaka, T.; Kawase, T.; gda, M, Tetrahedron

SECTION

202: ALKENES

Belier. aFischer,

SECTION

H.; Kiihlein,

203: ALKENES

n

FROM

AMINES

K. Tetrahedron

FROM

Lett., 1993, 34, 3445

Lett., 1994, 35, 8773

ESTERS

1% Pdz(dba)3-CHC13 ,2.2 HCOOH 2% chiral phosphine , dioxane 1,8-his-(dimethylamino)naphthalene 20°C ,22h :

%, ++H MeO,CO Me 96% (85% ee, R) . T,; Iwamura, H.; Naito, M.; Matsumoto, Y .; Uozumi, Y .; Miki, M.; Yanagi. J. w. Am. Chem. Sot.., 1994, 116, 775 02

Section 205

SECTION

AIkenes from Halides

204:

ALKENES FROM THIOETHERS

221

ETHERS,

EPOXIDES

Te , THF

OAc

I

OH

LiBHEt3 c Ph Ph DC,; Zhang, Y.; Discord& R.P. J. Org. Chem., 1994, 59, 1004

uenishi. J,; Kubo, Y. Tetrahedron

A

65%

Lett., 1994, 35, 6697

set-BuLi , -78OC+ rt ,90 min 76%

Bu

Bu

Gr

Doris, E.; Deschoux, L.; Mioskowski,

SECTION

AND

205:

ALKENES

C. Tetrahedron

FROM

Bu

Lett., 1994,

HALIDES

Bu 3.5, 7943

AND SULFONATES

Bu$nH , AIBN , Tol, reflux Ph Destabel,C.; Kilbum, J.D. Knight, J. Tetrahedron Lett., 1993, 34, 3151 9

.

nI

..Li,TI-IF,rt,lh 2. ZnCl;!, THF , O°C-+ rt Br

w , THF ,66OC

m. 1993,

5% “Pd(PPh3)2” , 1Oh T&; Gilbert, A.M.; Huttenloch, M.E.; Min-Min, G.; Brintzinger, 34,

3551

H.H. Tetrahedron Lett.,

Compendium

222

Br

Me$i

of Organic Synthetic Methods, Vol. 9

MeLi,

Section 206

20°C 82%

-A %k siMe3 Br Bu Bu Baird. M.S; Dale, C.M.; AI Dulayym, J.B. J. Chem. Sot., Perkin Trans. I., 1993, 2

c14H16’-

eq. MezS=CHz

, THF

L,

1373

C14h6

92% -1OOC + It AIcaraz, L.; Hamett, J.J.; Mioskowski, C.; Martel, J.P.; Le Gall, T.; Shin, D.-S.; Falck, J.R. Tetrahedron Lett., 1994, 35, 5453 Br

1. CuCN.2 LiCl , DMPU CSH

17Zd

C8H1-

2. E-hexenyl iodide, 60°C ,12h

Bu quant.

Marquais, S.; Cahiez, G.; Knochel. P,Synlett, 1994, 849 Br Ph L WR.;

SmI2,THF,5min

Ph

= i Br Bessho, K.; Yanada, K. Chem. Lett., 1994, 1279

r

I Bu 3SnHPh

*

Phm

/

10% Pd/C , 10% CuI ,20% AsPh3 NMP , 80°C 75 Me0 Me0 Roth, G.P.; Farina, V.; Liebeskind, L.S.; Pena-Cabrera, E. Tetrahedron

C; Aronica, L.A.; Lardicci, L. Tetrahedron

SECTION

206: ALKENES

FROM

Ph

I

82%

Lett., 1995,

EtMgBr , THF , O°C

MaIan=

Ph 95%

36,

quant. Lett., 1995, 36,9189

HYDRIDES

For conversions of methylenes to alkenes (RCH2R’ + 200 (Alkenes from Alkyls). NO ADDITIONAL

EXAMPLES

RR’C=CH2),

see Section

2191

Section 209

223

Alkenes from Alkenes

SECTION

207: ALKENES

FROM

KETONES

65%

PhMe , 50°C

Me

Petasis. N.A; Bzowej, E.I. Tetrahedron

Lett., 1993,

34,

943

(Me0)2POCHgO2Me 0

(-)=yo2t% LiOH , THF , MS , reflux ,4h5c Cardilli, A.; Lattanzi, A.; Orelli, L.R.; Screttri. A, Tetrahedron

wsz; 3383

t-B+(-)=o -a.

$ ~~;;f;;~r2*

t-Bu-(-)=
newDiels-Aldercatalyst Kobwashi. S,; Hachiya,I.; A&i, M.; Ishitani,H. Tetrahedron Lett., 1993, 34, 3755

OTBS

ArN=Mo(OR)=CHRcatalyst

OTBS

PhH, 20°C,30 min 91% Fu, G.C.; Grubbs. R.H,J. Am. Chem.Sot., 1993, 115, 3800 2

Ph-

1%Mo[OC(CF&Me]2(NAr)CHCMe2Ph * pl/%/+c6HD

+

89%

W-h~

Qowe. W.E,; Zhang,Z.J. J. Am. Chem. Sot., 1993, 115, 10998

&

1.PhBr , THF , Pd(PPh& NaOH , reflux , 12h 2. NaOH, Hz02

P –

8,

siM!e3

L&t., 1994, 35, 27 w17

SmI2 PhH/HMPA, rt , 10min

Ph

aI’ O-l/ ()/\ w-h7

83%

siMe3

J.&; Colbert,J.C. Tetrahedron

I I J

k

* d

Kunishima,M.; Hi&i, K.; Tani, S,; Kato, A. Tetrahedron

Ph

76%

Lett., 1994, 35, 7253

8%(PCy3)g1,Ru=CHCH=CPh2 PhH ,55”C, 3h

Miller, S.J.; Kim, S.-H.; Chen,Z.-R.; Grubbs.R&J. Am. Chem. Sot., 1995, 117, 2108

Section 210

Alkenes from Misc.

225

(96.

4)

44%

W,; Schrisder, F. Tetrahedron Lett., 1994, 35,7935

B

Ni(dppe)Clz,iPrMgBr , THF Me$iCl , rt , (seconds)

Ma1 _

,; Urso,A.; Lardicci,L. Tetrahedron L&t., 2995, 36, 1133

Ar = 2,4-dibromophenyl 68%(97%ee) ; Calabrese, J.C. J. Am. Chem. Sot., 1995, 117, 8992 REVIEW:

“Reagent-Controlled AsymmetricDiels-AlderReactions,”Qh.T,; Reilly, M. Org. Prep. Proceed. Int., 1994, 26, 129

SECTION

r

210: 0 II 0888q pN t-Bu

ALKENES FROM COMPOUNDS

MISCELLANEOUS

1. BuLi , THF , -78OC 2. 4.C EtI1lH23C&Me 3. KOt-Bu

CllH23

-Y 5. CeC13,NaBH4 6. THF, 105OC,20h 63x%x93x92% (102:1 E.-Z) Denmark. S.E,; Amburgey,J. J. Am. Chem. Sot., 1993, 115, 10386

226

Compendium of Organic Synthetic Methods, Vol. 9

2% Pd(acac)z , BuLi , THF , reflux *

Section 210

vGoH21

70%

Gai, Y.; Jin, L.; Jnlia. M.: Verneaux. J.-N, J. Chem. Sot. Chem. Commun., 1993, BuLi

9 2%

1625

Wa~d3

O°C +

reflux

+

C3H7-C3H7 79% (76:24 E.-Z)

Jin, L.; Julia. M.; Verpeaux, J.N. Synlett, 1994, Ph-s-

215

KOH , Al203 , CBr2F+BuOH

Ph

t

Phm

02

Ph

96% (Ihan. T.-L,; Fang, SF.; Li, Y.; Man, T.-O.; Poon, C.-D. J. Chem. Sot. Chem. Commun., 1994, 1771

Ph

02Ph

4

8 eq. SmI2, THF , DMPU 35 min

*

PhwPh

95% Ph Keck. Cr.E,; Savin, K.A.; Weglarz, M.A. J. Org. Chem., 1995, 60, 3194

OEt s6 II

Shimagaki.

.OEt

(E:Z 9:l)

Lawesson’s reagent, xylene *

reflux ,22h

CgH1gwC$117

quant. Lett., 1995, 36 719

0 M,; Fujieda, Y.; Kimura, T.; Makata, T. Tetrahedron Mg” , cat. HgC12, EtOH SO2Ph

5 rt ,2h

Lee, G.H.; Lee, H.K.; Choi, E.B.; Kim, B.T.; Pak, cI.S, Tetrahedron REVIEW: “Rare Earth Metal Trifluoromethanesulfonates as Water-Tolerated Organic Synthesis,” Kobavashi. S, Synlett, 1994, 679

Let?., 1995,

98% 36,

5607

Lewis Acid CatIaysts in

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

Oxides from Alcohols

Section 213

CHAPTER

227

15

PREPARATION

OF OXIDES

This chapter contains reactions which prepare the oxides of nitrogen, sulfur and selenium. Included are N-oxides, nitroso and nitro compounds, nitrile oxides, sulfoxides, selenoxides and sulfones. Oximes are considered to be amines and appear in those sections. Preparation of sulfonic acid derivatives are found in Chapter Two and the preparation of sulfonates in Chapter Ten.

SECTION

211: OXIDES

FROM

ALKYNES

1. ClPPh2 , NEt3 , THF , -78°C

-coMe

; Slattery, B.J. Tetrahedror~~k~.,1994, 35, 5137

SECTION

212: OXIDES

0 I

FROM

ACID DERIVATIVES SnMe3

SO2Cl Me

*

PhCl, 130°C

/

Me

2d

Neumann.W.P,; Wicemec,C. Chem. Ber., 1993, 126, 763

SECTION

213: OXIDES

FROM

ALCOHOLS

>(

0

I , -40°c 0 CH2C12 2. air

AND THIOLS

1. -S-l Gu, D.; m

IIN, Tetrahedron

Lett., 1993, 34, 67

-so$-I

74%

228

Compendium

SECTION

214: OXIDES

of Organic Synthetic Methods, Vo19

FROM

ALDEHYDES

NO ADDITIONAL

SECTION

215:

OXIDES ARYLS

FROM

EXAMPLES

ALKYLS,

NO ADDITIONAL

SECTION

216: OXIDES

FROM

217: OXIDES

Ph-

NI OH

Ph

FROM

METHYLENES

AND

EXAMPLES

AMIDES

NO ADDITIONAL

SECTION

Section 219

EXAMPLES

AMINES

0,05 Pr4N Ru04 , 1.5 NM0

b

Ph*?-

Ph I %

MeCN,rt,2d

75% (>50:1 ZE) Goti. A,; De Sarlo, F.; Romani, M. Tetrahedron

L&t., 1994, 35, 6571

H2N-(=)-co2H ,““” * Webb. K&;

Seneviratne, V. Tetrahedron

Lett., 1995, 36, 2377

SECTION

218: OXIDES

ESTERS

FROM

Na$02Tol, THF 0.01 Pd(PPh3)4, rt i)Ac

chiral phosphine ,72h

S02Tol

..

(10 Eichelmann,

H.; M.

SECTION

219:

H.-J, Tetrahedron

OXIDES FROM THIOETHERS

S

Guertin, K.R.; -de.

L&

OS(=O)Tol 1) 83%

Asymmetry, 1995, 6, 643

ETHERS,

5% TPAP ,3 eq. NM0 MeCN , 30°C, 4A MS ,2h 0

+T

EPOXIDES

w

TPAP = (n-Pr)fl Ru04 Tetrahedron Lett., 1993, 34, 5369

AND

92%

Section 219

Oxides from Ethers

WW4,

229

hv (Pyrex)

7I

PhHsAMe PhHsL

CH2Q

Me

92% Ramkumar, D.; $3.nkararaman. S, Synthesis,

1057 ?I

H202, MeCN , K2C03

PhHS-Me Page. PC&,

1993,

PhHs-

Me 82% MeOH, O°C ,2h Graham, A.E.; Bethell, D.; Park, B.K. Synth. Commun., 1993, 23, 1507 Mn02, Me3SiC1, MeOH

Ph–‘,Me

0 II 99% S ’ Me 23, 1759

w Ph.

Bell&a, F.; Ghelfi. F,; Pagnoni, U.M.; Pinetti, A. Synth. Commun., t-BuOOH, H20, 70°C, 30min BuHS,

*

Bu

1993,

0 II

B/N Bu J+inmelli. F,; Pellegrino,R.; Pizzo, F. Synth. Commun., 1993, 23, 3157

quant.

0

cyclohexanone monooxygenase w

Ph?*

II Ph/‘*

73%(99%ee, R) Secundo,F.; Carrea.G,; Dallavalle,S.; Franzosi,G. Tetrahedron Asymmetry, 1993, 4, 1981 1.35eq.oxone * rt, 1.2h with 0.65eq.Oxone- obtain47%sulfoxide We&J&

Tetrahedron

Lett., 1994, l

‘44

1.1

83%

35, 3457

P

$3F3

.N + F

0

II 95% CHC13, CFC13, -40°C ph/s with 2.7 eq.,obtainthe sulfone(91%) DesMarteau.D.D,; Petrov, V.A.; Montanaari,V.; Pregnolato,M.; Resnati.G, J. Org. Chem., 1994, 59, 2762

ph/s

C4F9

*

230

Compendium

of Organic Synthetic Methods, Vo19

NaI04, cat. RuC13eH20 Ph-‘-

Ph

Su. W. Tetrahedron

Section 219

0

/

0

NH Ph-S-Ph

lh Lett., 1994, 35, 4955

quant.

NHAc &

mcpba

*

NHAc

xfx

+x)c

C

.

(8 Glass. R&; Singh, W.P.; Hay, B.A. Tetrahedron

1. Ph/SIMe

I

3)

Lett., 1994, 35, kO9

H202, ether, DBU , -28OC (-)-camphorsulfonylimine 1

2. aq. Na sulfite Me. P.CB,; Heer, .J.P.; Bethell, D.; Collington, 1994, 35, 9629

quant (35% ee, R) E.W.; Andrews, D.M. Tetrahedron Lett.,

NaOCl , TEMPO,

Ph”,

Me

[email protected] , CH#X2,

KBr

0 II

* PhHs,

satd. NaHCO3

Me

87% Siedlecka, R.; Skarzewski.

J, Synthesis, 1994, 401 0 II

PhIO , cat. TsOH , MeCN ,25OC *

Ph/‘Me . . avlca

.

82%

Ph/‘Me G, Synth. Commun., 1994, 24, 2223 1. Mn02-35% aq. HCl , MeOH 0°C + 10°C, 0.75h

Pl?

0 II

t

Me

99%

2. NaOH Ph/‘lMe Fabretti, A.; Ghelfi, F.; Grandi. R,; Pagnoni, U.M. Synth. Commun., 1994, 24, 2393 NaBQ Ph /‘-Me

, II, wet zeolite F-9

0 w

II

CH2C12, lh PhRSNMe Hirano, M.; Kudo, H.; rvl[orimoto. T, Bull. Chem. Sot. Jpn., 1994, 67, 1492

82%

Section 219

Oxides from Ethers

231

PhIO , MeCN , lh 10% Mn salen catalyst

Ph-‘lMe

0 II ‘-Me

PF

57% (62% ee, R) Noda,K.; Hosoya,N.; Irie, R.; Yamashita,Y.; J(atsuki.T, Tetrahedron, 1994, 50, 9609

p-Tel/

‘+Me

0 II HS-Me p-To1

chiraloxaziridine, CHg12 t o”c

70% ee W .B,; Kochanewyczm,M.J.; Lovely, C.J.; Boyd, D.R. J. Chem. Sot. Chem. Commun., 1994, 25 69

PhMezCOOH, Ti(OiPr)d, Hz0 PhjSIMe

77% (99% ee,R)

II

*

S

(RR)-DET, CH2C12,-2OOC Ph’ ‘Me Brunel,J.-M.; Diter, P.; Duetsch,M.; Kag;ln. HB, J. Org. Chem., 1995, 60, 8086 1.5M HNO3,1% FeBq ,30 min

0 II

*

B+Bu

84%

B/Bu Sutiez, A.R.; Rossi,L.I.; Martin, S.E. Tetrahedron Lett., 1995, 36, 1201

B4s

SiO2, CH2C12,t-B&OH > Bu 30min

0

II S Bu’ ‘Bu

86%

with 2 eq. t-B&OH, obtain83%of sulfone P.J, Tetrahedron Lett., 1995, 36, 3825 Breton,G.W.; Fields,J.D.; m. cyclohexanone monooxygenase *

PhAS’

Pasta.P,; Carrea,G.; Holland,H.L.; Dallavalle,S. Tetrahedron

PhHs,

Me

Nagata,T.; -K.;

Ph-S’ II

0 97% (54% ee, R) Asymmetry, 1995, 6, 933

0

02 , m-xylene, Mn (III) salencomplex t

II

66%(51%ee) t-BuCHO, rt Me Yamada,T.; Mukaiyama,T. Butt. Chem. Sot. Jpn., 1995, 68, 3241 Ph”,

232

Compendium of Organic Synthetic Methods, Vol9

SECTION

220: OXIDES

FROM

HALIDES

Section 222

AND SULFONATES

Phi , CuI , DMF , heat PhS02Na Suzuki. H,; Abe, H. Tetrahedron Lett.,

SECTION

221: OXIDES

a 1995,

FROM

36,

PhSO$‘h

6239

HYDRIDES

NO2-03, CH2C12 *

Me -1OOC ,3h

a; M. From

. . .

51%(57:2:41o:m:p) Murashima,T.; Kozai, I.; Mori, T. J. Chem. Sot., Perkin Trans. I., 1993, 1591 It; Mori, T. J. Chem. Sot., Perkin Trans. I., 1995, 29 1 aryl

Suzuki.; From

.

aryl

Suzuki.;

esters:

meta-nitro

is the

major

product

Tomaru,J.-i.; Murashima,T. J. Chem. Sot., Perkin Trans. I., 1994, 2413 acetates:

ortho:para

predominates

(60:40)

Tatsumi,A.; Ishibashi,T.; Mori, T. J. Chem. Sot., Perkin Trans. l., 1995, 339 NO2-03, MeCN, MgO , O°C

R = Et R=H

95% (14:31:55 0:m:p) 0% . &&,l, H; Yonezawa,S.; Mori, T. Bull. Chem. Sot. Jpn., 1995, 68, 1535 REVIEW:

“Ozone-MediatedNitrationof AromaticCompounds with LowerOxidesof Nitrogen,”Mori, T.; &z&i. K Synlett, 1995, 383

SECTION

222: OXIDES

J5 Olah, GA.;

0

FROM

KETONES

1. NH20H, PtCl , KOH NO2

2. CF3C03H

(1113exo:endo) Ramaiah,P.; P&ash. CKS, J. Org. Chem., 1993, 58, 763

60%

Section 225

SECTION

Oxides from Misc.

223: OXIDES

FROM

233

NITRILES

hv (254 nm) SO2Ph Li, C.; Fuchs. P.L Tetrahedron

SECTION

224: OXIDES

55%

MeCN ,25,C, 2h Lett., 1993, 34, 1855

FROM

ALKENES

Et* 0-N& EtO’, 0

9 Bu$nH

toluene, AIBN (syringepump)

mBu

EtO -Bu EtO-[, 0

Balczewski,P.; MikoIajczyk, M. Synthesis, 1995, 392

SECTION

225:

OXIDES FROM COMPOUNDS

72%

MISCELLANEOUS

PhMgBr, THF ,25OC

*

71%

i?h Cardellicchio,C.; Fiandanese, V.; Naso.F,; Pietrusiewicz,KM.; WSewski,W. Tetrahedron Lett., 1993, 34, 3135

PhCHO t cDc13

Oe5M

Me2N

t-Bu + Me2N

Denmark.SE,; Griedel,B.D.; Coe,D.M. J. Org. Chem., 1993,*58, 988

t-Bu

234

Compendium of Organic Synthetic Methods, Vo19

PhO#

Ph

7

Section 225

S02Ph 1. LiNAPH

2.

Br-

. . Yu, J.; Cho, H.-S.; Chandrasekhar, S.; Falck. J.R… Mlmkours)sl. (1, Tetrahedron 35,5437

Lett., 1994,

0

0 THF,l-t

Cardellicchio, C.; Fiandanese, V.; mo. Tetrahedron Lett., 1994, 35, 6343

F,; Pacifico, S.; Koprowski,

61% (>98% ee, S) M.; &&u.&wicz. K.M.

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

Section 302

AIkyne – Alcohol

CHAPTER

235

16

PREPARATION COMPOUNDS

OF DIFUNCTIONAL

SECTION 300: ALKYNE – ALKYNE 1. NaNTMS2 ; NBS ~~~‘~~~~-Bu

Maeriotis. P.pL; Vourloumis, D.; Scott, M.E.; Tarli, A. Tetrahedron L&t., 199;, 34, 2071

SECTION 301: ALKYNE – ACID DERIVATIVES NO ADDITIONAL EXAMPLES

SECTION 302: ALKYNE – ALCOHOL, THIOL

vCHO Brown.;

Lo- 1. Bu$nI , -85OC+ 2.3 eq. ZnC12

MsO

82%

ether, 25OC, 15 min 2. H202, NaOH Khire, U.R.; Racherla,U.S. Tetrahedron Lett., 1993,34,15 % +9 %

O°C

3.iPqCHO -*

OH

Bu 89% (98:2 antisyn)

Katsuhira, T.; Barada. T,; Maejima, K.; Osada,A.; Qku. A, J. Org. Chem., 1993, S&6166

Compendium of Organic Synthetic Methods, Vo19

236

Section 302

.

(94

6) 80% Zhang, L-T.; MO, X-S.; Huang, J-L.; Huang. Y.-Z< Tetrahedro;r Lat., 1993, 34, 1621 00

0, 0

1.2 eq. LDA, THF, -1OOOC 2.2 eq. PhCHO , THJ?

p-To Y

3. NaH ,THF , O°C

I z

H

siAk3

Kusuda, S.; Kawamura, K.; Ueno, Y.; Toru.

0

Ph 83% (>99%ee, S) Tetrahedron Let?., 1993, 34, 6587

1.3 eq. t-BuLi 2. EtCHO , -78OC +

II Ph.

-3OOC *

k Ph Cl Satoh, T.; Hayashi, Y.; Yamakawa.

;>ePh 67%

Bull. Chem. Sot. Jpn., 1993, 66, 1866

1. o-DCB , reflux

w

2. TBAF

Jin, J.; Smith, D.T.; weimb.

SK

J. Org. Chem., 1995, 60, 5366

(PhCd&AlEt2’

Na+

PhCHO To1 , O°C , lh

)

Ph>ePh

OH Ahn, J.H.; Joung, M.J.; Yoon. N.M, J. Org. Chem., 1995, 60, 6173

95%

Bu-Bu C8HlY

I

SmI2, HMPA/PhH

Bu 78% Kunishima, M.; Tanaka, S.; Kono, K.; Hioki, K.; Tani, S, Tetrahedron Let?., 1995, 36, 3707

Alkyne – Amine

Section 305

237

t-BuCHO , Ga13, NEt3 Ph

=

H

Pl?

=

TfWfi 80% Han, Y.; Huanae. Y.-7, Tetrahedron L&t., 1995, 36, 7277 Ph

=

SnBu3

+

PhCHO

;>el’h

InC13 , MeCN ,25OC ,30 min 92% Yasu&, M.; Miyai, T.; Shibata, I.; Baba, A,; Nomura, R.; Mats&a, H. Tetrahedron Let?., 1995, 36,9497 PhCHO , Zn , THF

+ satd. NH&l,

Ph>

Phx

rt

.

(89 -I.;

Riazi-Kermani,

F. Synth. Commun., 1995, 2.5,

SECTION 303: ALKYNE SPh

2923

11) 68%

l

– ALDEHYDE 1. s02C12,

cc4, o”c

Fortes. CC;

+ PWCHO 2. CuC12, [email protected] Garrote, C.F.D. Synth. Commun., 1993, 23, 2869

SECTION

304: ALKYNE

47%

Ph—==—-/

– AMIDE NO ADDITIONAL

EXAMPLES

SECTION 305: ALKYNE – AMINE 2 Et2NH2, 1% CuCl

(““”

THF , 50°C, 2h Imada, Y.; Yuasa, M.; Nakamura, I.; &&K&K&. F2B

WuJJ.-L;

=

.

NEt2

S.-L J. Org. Chem., 1994, 59, 2282

SiMe3

/

OH

Yan, D.-S.; Tsai, H.-W.; Chen, S.-H. Tetrahedron Let?., 1994, 35, 5003

91%

238

Compendium of Organic Synthetic Methods, Vol9

BuNH2,3%

gBr

Section 307

CuBr , MeCN b

90%

Geri, R.; Polizzi, C.; Lardicci, L.; Qporusso. A.m Gazz. Chim. Ital., 1994, 124, 241

Okita, T.; hobe. M, Tetrahedron, 1995, 51, 3737

SECTION

306: ALKYNE

– ESTER NO ADDITIONAL

SECTION

Phu

307: ALKYNE

– ETHER,

EXAMPLES

EPOXIDE,

THIOETHER

!-c) PhSeSePh L

* Ph- CZC-SePh 75% CuI , HMPA Reckziegel, A.; Menezes, P.H.; Stefani, H.A. Tetrahedron Let?., 1993, 34, 393

=C-Br &;

PhSeBr , CuI , DMF W-4

a

-H

C5H,lpSPh

82% Silveira, C.C.; Reckziegel, A.; Menezes, P.H. Tetrahedron Let?., 1993, 34, 8041

Braga. a;

PhI(OAc)2, PhSeSePh , CH2C12 Ph

w

=

Ph

=

SePh

4o”c 81%

Tingoli, M,; Tiecco, M.; Testaferri, L.; Balducci, R. Synlett, 1993, 211

0I / HO

OCOCF3

, MeCN

DBU , CuC12e2H20 , O°C

0

// 4

83% Godfrev U-D,; Mueller, R.H.; Sedergran, T.C.; Soundararajan, N.; Colandrea, V.J. Tetrahedron Let?., 1994, 35, 6405

Section 311

SECTION

Alkyne – Alkene

308: ALKYNE

239

– HALIDE

k:

1;;

&&velm

V,; Rollin, Y.; G&&henne, C.; Gosmini, C.; P&ichon, J. Tetrahedron L&t.,

1994, 35, 4777

(collidine)$

P-H Brunel, Y.; JXouw. SECTION

PF6

t

Ph

=

I

75%

G, Tetrahedron Lett., 1995, 36, 2619

309: ALKYNE

– KETONE

J-c Cl

‘*

Ph

0

7NW *

2. FVP (5OO*C) ~R.A.;

PlPh

72% x 82%

H&ion, H.; Janosi, A.; Raut, S.V.; Seth, S.; Shannon, I.J.; Smith, F.C.

Tetrahedron Lett., 1993, 34, 5621

SECTION

310: ALKYNE

– NITRILE

1. CuCN , TMSCl , H20 DMSO , MeCN ,72h P-H

t

2. cat. NaI , 50°C uo. F.-T%;Wang, R.-T. Tetrahedron Lett., 1993, 34, 5911

SECTION

311: ALKYNE 2

P-CN

72%

– ALKENE 10% Pd(OAc)2, 30% PPh3 THF , reflux , lh

% &Iandai. T,; Tsujiguchi, Y.; Matsuoka, S. Tetrahedron Lett., 1993, 34, 7615

96%

Compendiumof Organic Synthetic Methods, Vol9

240

Section 311

co Et

SiMe3

2

Pd(dba)z, Ph3As NMepyrrolidone , 40°C

OTf

90%

2, aq. HCl B.H,; Alami, M. Tetrahedron Lett., 1993, 34, 1433

mhutz.

0.05 Pd(PPh)4, 0.1 CuI 2eq.N&,PhH,lh Gueugnot, S.; Linstrumelle, G. Tetrahedron Lett., 1993, 34, 3853

w-h

1 5

.

Alaml.;

I

/–OH

c5

11

, Pd(PPh3)4,15min

0

M Ferri, F.; m.

*

H

93%

G, Tetrahedron Lett., 1993, 34, 6403

1. norbomadiene, Bu3Sn = Ph 1% PdC12(PPh3)2,80-100°C, 20h Phi 2. heat

Ph

Kosuni. M,; Kimura, T.; Oda, H.; Migita, T. Bull. Chem. Sot. Jpn., 1993, 66, 3522 1. Cfl 11, Pd(PPh3)4, CuI

A

Cl a;

.

Cl

2. PdC12(PhCN)z,piperidine rt

Crousse,B.; Linstrumelle, G. Tetrahedron Lett., 1994, 35, 3543

phtph n. It&;

FVP (500°C)

Boeters, C.; Morrison, J.J. J. Chem. Sot., Perkin Trans. l., 1994, 2473

59%

Section 314

Acid – Aldehyde

SiMe3

C

241

Me3Si 1. set-BuLi , THF , -45OC 2.ZnBr2 -45OC + 20°C

SW3

s

3. H30+ SiMe3

-8-

85%

I… Nonnant. J.-F,; Platzer, N. Tetrahedron Lett., 1994, 35, 5645

Meyer, C.; u

Ph Ph 5% HRh(CO)(PPh3)3 35% PEt3 Bu

Z

H+ THF , reflux ,9h 68% (>20: 1 endo:exo)

Yamzguchi. M,; Omata, K.; Hirama, M. Tetrahedron Lett., 1994, 35, 5689

Ph

x

SnBu3

, Dibal , THF

YCl

Ni(acac)z , P(OEt)3 yrefiux 77% Cui, D.-M.; Hashimoto, N.; Ikeda. S,; Sato, Y. J. Org. Chem., 1995, 60, 5752

SECTION 312: CARBOXYLIC

ACID – CARBOXYLIC

NO ADDITIONAL

SECTION 313: CARBOXYLIC

ACID

EXAMPLES

ACID – ALCOHOL,

THIOL

1.1:3 TiCldLiAlH4, lh CFC13 , THF , -5°C 2. aq. HCl 62% Garcia, M.; de1 Campo, C.; Sinisterra, J.V.; Llama, E.F, Tetrahedron Lett., 1993, 34, 7973

SECTION 314: CARBOXYLIC

ACID – ALDEHYDE

NO ADDITIONAL

EXAMPLES

242

Compendium of Organic Synthetic Methods, Vol9

SECTION 315: CARBOXYLIC

Section 316

ACID – AMIDE

Me M&J4

44,

1.2.2 LDA , ZnC12 2. HJO+

0/ A 0 T

.

a.

9

*

FY

N w-r

0

H

cog-I 86% (88% de)

U+; Maier, S. J. Chem. Sot. Chem. Commun., 1995, 199 1

5 eq. LDA ,2.5 eq. Al(OiPr)3

0

70% (98% ds/86% ee) J(azmaier. ‘IJ,; Krebs, A. Angew. Chem. Int. Ed. Engl., 1995, 34, 2012

SECTION 316: CARBOXYLIC

0

A?–

ACID – AMINE

1. PhMgBr , THF , -40°C 2. TFA , CH2C12

C02Et

I BoC

3. DDQ , CH2C12 4.10% NaOH , reflux

C02H

-l+’ H

83~72~93% UJ.; Pedregal, C.; Rubio, A.; Valenciano, J.; Navio, J.L.G.; Alvarez-Builla, J.; Vaauero. u Tetrahedron Lett., 1993, 34, 6317

1. Ph//““”

w

OSiMe3

NHPh OSiMq

, ZnBr2, CH2C12 C02H

2. H30+ 84% (35:65 syn:anti)

]Mladenova. M,; Bellassoued, M. Synth. Commun., 1993, 23, 725

Section 318

Acid – Ether

243

Nc /“@Me~~~~h~~~~ep) (02H+ ‘“) (02H derivative, 25OC,40h 2.6N HCl

(94 T, Tetrahedron Lett., 1994, 35, 2713

Soloshonok, V.A.; m.

HO

NH2

Ho

NH2

.

6)

l

CO2H 1, oxaIy1chloride , ether 2. satd.NaHC03, refIux 3. TsNHNH2 , reflux 4. NaE3H4,THF

H

98×39% H

Guan, X.; Borcb=irdt,

Tetrahedron Lett., 1994, 35,3013

*

REVIEWS:

“RecentDevelopmentsin the StereoselectiveSynthesisof a-Amino Acids,” b&&r.

R-Q,

Tetrahedron, 1994,50, 1539

“RecentStereoselectiveSynthetic Approachesto P-Amino Acids,” Cole. IX,

Tetrahedron,

1994,50,9517

Section315 (Carboxylic Acid – Amide). Section344 (Amide – Ester). Section 351 (Amine – Ester).

RelatedMethods:

SECTION 317: CARBOXYLIC

ACID – ESTER

NO ADDITIONAL EXAMPLES

SECTION 318:

CARBOXYLIC THIOETHER

ACID – ETHER, EPOXIDE,

C02H ..

(85 1 0 Mead. K.T; Pi&& SK. Tetrahedron Let?., 1993, 34, 6997

C02H 15)

82%

244

Section 322

Compendiumof Organic Synthetic Methods, Vo19

SECTION 319: CARBOXYLIC OzH

b

ACID – HALIDE, SULFONATE

1.2.2 eq. see-BuLiKMEDA THF , -9OOC 2.4 eq. c13cc13 , THF , -78OC

3.4N HCl / F Moyroud, J.; Guesnet,J.-L.; Bennetau,B.; Mortier. J I

SECTION 320: CARBOXYLIC

ACID – KETONE 98% (>98% ee)

Na , n-C3H70H, reflux

Moody, H.M.; Kantein. B,; Broxterman,Q.B.; Boesten,W.H.J.; Kamphuis, J. Tetrahedron Lett., 1994, 35, 1777 0.5 C~(ClO4)24 Hz0 02, MeCN ,rt ,lO-15h **OH 0 &sy.

96%

J,; Belotti, D.; Bellosta, V.; Brocca, D. Tetrahedron Lett., 1994, 35, 6089 Also via: Section 360 (Ketone – Ester).

SECTION 321: CARBOXYLIC

ACID – NITRILE

NO ADDITIONAL EXAMPLES Also via:

Section 361 (Nitrile – Ester).

SECTION 322: CARBOXYLIC

ACID – ALKENE

1. CFz=CHLi 2. H30+

NC”

3 H O+ l

3

* *c02H

Tellier. F,; Sauvetre,R. Tetrahedron Lett., 1993, 34, 5433

60% (E)

245

Alcohol – Alcohol

Section 323

0.1 pcy3

,3 TESCI

zs g;*

lbkC~

A/ c3*&,’

c3H–[email protected]

Hanamoto, T.; Baba, Y .; Inanaga. J, J. Org. Chem., 1993, 58, 299

=o=’

MnZnBr’ether

;F

Duchsne. A; Abarbi, M.; Pamin, J.-L.; Kitamura, M.;

,!402H Noy~ri,

R. Synlett, 1994, 524

Section 313 (Alcohol – Carboxylic Acids). Section349 (Amide – Alkene). Section 362 (Ester- Alkene). Section 376 (Nitrile – Alkene).

Also via:

SECTION 323: ALCOHOL, THIOL – ALCOHOL,

PhCHO ,SmI2,*

ph%ph

+

THIOL

phhcHo OH 1%

97% in THF + 2.8 eq. HMPA 10% Shiue, J-S.; Lin, C-C.; J%ng. J-M, Tetrahedron Lett., 1993, 34, 335 ~3W~N)6

Bu

9 K2C03

Bu

t-BuOH , H20,12h

r

N 6

~J.A,;

60%

OH 89%

ODHQ

SiMe3

.

80%

) 9 OS04

HOK

SiMe3 (89% ee)

DHQ = dihydroquinidine ODHQ

Rane, A.M.; L6pez, C.J. Tetrahedron Lett., 1993, 34, 1893 AD-mix-P

phoN

-t-BuOH , H20, 0°C PhO&OH 95% Tetrahedron Lett., 1993, 34, 2267 Wang, Z-M.; Zhang, X-L.; SharPless.

246

Section 323

Compendium of Organic Synthetic Methods, Vol9

Me

Me Rh+2 cat. , Cs2CO3 , PhBr

OH Barrett. A.G.w; Itoh, T.; Wallace, E.M. Tetrahedron Mt., 1993, 34, 2233

2 Lebrun, A.; &my.

0

1.2 eq. SmBr2 2. Hz0

J-I,; Kagan.

90% Tetrahedron Lett., 1993, 34, 2311

DHQ-CLB Me3SmC$-i11

H

Me& 93%(71%ee,R) 6H Zargarian, D. Tetrahedron ktt., 1993, 34,

Okatnoto, S.; Tani, K.; &Q. F.: ~K.B.; 2509 1. Ph$iSH , NEt3, MeOH P

2. TBAF, AcOH

-,,i-lt/OH

+

..

(7 Brittain, J.; m.

pASH

1)

Y, Tetrahedron Lett., I993, 34, 3363 H20, 10 KBar , 60°C, Id *

QH E

93% (49% ee) Kotsuki. H,; Kataoka, M.; Nishizawa, H. Tetrahedron Lett., 1993, 34,4037 7

l%Os04,1%catalyst

catalyst = bis-dihydrquinolyl

Crispino, GA.; Jeong, K.-S.-; Kolb, H.C,; Wang, Z-M.; Chem., 1993, 58, 3785

derivative

87%

c

247

Alcohol – Alcohol

Section 323

H

OH

H 1.10% Cp$QCl;! , ether / 2.5 eq. EtMgCl ,25OC, 12h 3. 02,OK

Et

-cc-r

70% (98:2 syn:anti)

Hovevda. A.J&; Morken, J.P. J. Org. Chem., 1993, 58, 4237

,

1%OS04,l-t,3K2c&

OH

Oallyl

3 K3Fe(CN)6,3 MeSO$H2,

t-BuOH-Hz0 82% (39% ee, R) Am. Chem. Sot.,

Morikawa, K.; Park, J.; Andersson, P.G.; Hashiyama, T.; VJ. 1993, 115, 8463 1. Li powder, CH& 5% 4,4’-di-t-Bubiphenyl THF , -4OOC

CHO

H

H

2. H20 +Y

52%

Guijarro, A.; Yus. M, Tetrahedron Lett., 1994, 35, 253

(95

.

5)

93%

Adam. WJ Gevert, 0.; Klug, P. Tetrahedron L&t., 1994, 35, 1681 ’ OH AD-mix f3 , aq. t-BuOH , O°C phw

5r PhS

Ph

Walsh, P.J.; Ho, P.T.; King, S.B.; wss.

+ OH (98% ee, 2S,3R) K.B. Tetrahedron Lett., 1994, 35, 5129

Ph 75%

Section 323

Compendium of Organic Synthetic Methods, Vo19

248

+wph

+

*o/

Jph

955 synmi O (94% ee, syn)

21%

50% ee, S

H Kaneko, Y.; Matsuo, T.; I(,ivooka. S, Tetrahedron Lett., 1994, 35, 4107

Yb-TMS-Br

OTMS

)

fl!p

62%

THF-HMPA TMSO ; Nakahashi, M.; Kuno, T.; Tsuno, M.; Makioka, Y.; I&&i. Tetrahedron Lett., 1994, 35,411l .

.

K.: Fujiwam Y,

0 t-BUSH, hv

)

K

C6H13U

Me

57% (4:l syn:anti) Newcomb. M,; Dhanabalasingam, B. Tetrahedron Lett., 1994, 35, 5193 Ph

0.1 Kz0~04 ,3 MeSOflH2

K3k(cN)6

,3 K2C03

OH

O°C , 12h

R = cinchonidine Corey. EJ.; Noe, M.C.; Grogan, M.J. Tetrahedron Lett., 1994, 35, 6405 NbC13, THF , rt 2 t-BuCHO

t

71% (>95:5 d,l:meso) zvmoniak. J,; Besangon, J.; MoIse, C. Tetrahedron, 1994, 50, 2841

Alcohol – Alcohol

Section 323

Al,KOH,MeOH,rt,5min

+

PhCHO

249

87% (1:l d,l:meso)

Ph Ph

OH Khurana. J.M,; SehgaI, A. J. Chem. Sot. Chem. Commun., 1994, 571 1. dIpczBH , ether , -78OC 2. PhCHO , -78OC *

3. NaOH , Hz02

PhL

= = AH

76% (>95% ee)

Brown. H.C,; Narla, G. .J. Org. Chem., 1995, 60, 4686 P$

*n l

&N,

H

Ph

Ph/

+

Ph e

H

/O

B

Ph

H

* BH3, THF

0

Ph 3 OH (16% meso:RR+SS (99% ee SS)

Quallich. G.J,; Keavey, K.N.; WoodaIl, T.M. Tetrahedron Lett., 1995, 36, 4729 CHO

C

CHO

Bu$nH , PhH ,2O”C hv

ta

OH OH

46% (98: 1 cixtrans)

Hays, D.S.; Fu. G.C, J. Am. Chem. Sot., 1995, 117, 7283 Ph

es 9 t-BuOH , H20, &Fe(CN)e

* Ph K2CO3, (DHQDhPHAL , K~OSO~)OH)~

OH 95% (97% ee , R)

Torii, S.; Liu, P.; Tanaka, H. Chem. Lett., 1995, 319 REVIEWS:

“Synthesis of cr.,@-Alkenediols.A Review,” Patwardhan.S.A, Org. Prep. Proceed. Ink, 1994, 26, 645

Section 325

Compendiumof Organic Synthetic Methods, Vol9

250

“The Oxygenation of Vinyl Cyclopropanesas an Entry Into Stereoselective1,3-Diol Synthesis,” Feldman. Synlett, 1995, 2 17 “Catalytic Asymmetric Dihydroxylation,” Kolb, H.C.; Van Nieuwenhze, M.S.; SharPless. K.B. Chem. Rev., 1994, 94,, 2483

Also via:

Section 327 (Alcohol – Ester).

SECTION 324: ALCOHOL,

Section 357 (Ester – Ester).

THIOL – ALDEHYDE

1. PhCHO , NEt3 *

II-CHO

+)-cO2H

2. H30+ I

51% Barco, A.; Benetti, S.; De Risi, C.; Pollini, G.P.; Spalluto, G.; Zanirato, V. Tetrahedron Lett., zp

34, 3907

1993,

[RhCI(CO)& , 1-methylpyrazoIe HSiMe2Ph , CO (50 atm) Fukumoto, Y.; Chatani, N.; Murai. S, J. Org. Chem., 1993, 58, 4187 0

9vp)c cs /“7

Ph$=CHOMe , CHCl3,2X

*

CHO

C6H13

Yu, L.; u

C6H13

QH s = = -CHO

77%

ZAJ. Chem. Sot. Chem. Commun., 1993, 232

Section 330 (Alcohol – Ketone).

RelatedMethods:

SECTION 325: ALCOHOL,

mo2

NA Cl

THIOL – AMIDE

1. EtCHO , Li(powder) 3% C1()Hg,THF 2. H20 *

m-92N

w

71% OH

Ram6n, D.J.; Yus. M, Tetrahedron Lett., 1993, 34, 7115 NHTs 3

m.

aq.NaOH, 100°E (-h

.

J,; Bats, J-P.; Hautefaye,P.; Nuhrich, A.; Lamidey, A-M.

Tetrahedron Lett., 1993, 34, 2315

,o~5%

Section 325

Alcohol – Amide

251

H

MeS02NH2, t-BuOH , Hz0 rt , AD-mix-pTM *

mt

Ph

2

96% (96% ee)

v

mt2

OH AD-mix-pm= 5% DHQDz-PHAL (chichona alkaloid-phthalzine reagent),2% K~OSO~(OH)~ Bennani, Y.L.; -less. KB, Tetrahedron Lett., 1993, 34, 2079 COzMe

1. Dibal , -78OC 2.

NHCbz

OTMS

H OMe 3. TiCl2(OiPr)z

.

H

*A

CO&k

= = = I

+

NHCbz

CO2Me

2s

66%

10%

K yooka. S.; Suzuki, K.; Shirouchi, M.; Kaneko, Y.; Tanimori, S. Tetrahedron Lett., 1993, 34, 5;29

HO Me2CuLi , Me (96 Reetz. M.T,; Riilfing, K.; Griebenow, N. Tetrahedron Lett., 1994, j5, 1969

1. BuLi , -78°C 2. LiNaphth , -78°C

pBz

3. PhCHO

me2

FHBz

p +

(1 Foubelo, F.; Yus.

4)

84%

OH

!Ph

..

1) 72%

Tetrahedron Lett., 1994, 35, 4831

1. LDA , THF , -78°C 2. CeC13,THF , rt

* PhnfMe2 3. PhCHO , THF , -78OC 0 OH Shang, X.; Liu. H.-J,Synth. Commun., 1994, 24, 2485

0

68%

. H 3) 66% (97 Taniguchi, M.; Fujii, H.; Oshima. K.: Utimoto, K, Bull. Chem. SO;. Jpn., 1994, 67, 2514

252

Compendiumof Organic Synthetic Methods, Vol9

Section 326

hv

Nfw-b3

-G

c

0 HO

jJ

86%

0 w-h3 Dlttarm., Xu, F.; Qi, H.; Martin, M.W.; Bordner, J.; Decosta,D.L.; Kiplinger, J.; Reiche, P.; Ware, R. Tetrahedron Lett., 1995, 36, 4197 .

.

CL

(CHzO), , acetone, K2CO3 ) ON 0 N 0 N H20, ultrasound I H d OH Jouglet, B.; Oumoch, S.; Rosseau.G, Synth. Commun., 1995, 25, 3869

SECTION 326: ALCOHOL,

B

[email protected]

96%

THIOL – AMINE

1. LDA , TiC12(OiPr)2 THF * 2. t-BuCHO , THF 3. H30+

Et02C&ph

+

Et02Aph

6H

Ph

(>99

OH :

1)

78%

jf

KanemasaI S,; Mori, T.; Wada, E.; Tatsukawa,A. Tetrahedron Lett., 1993, 34,677 OH Ph Ph

2 TsNCO , THF , Id 2% Pd[P(OiPr)&

reflux OH

Xu, D.; -less.

K.B Tetrahedron Lett., 1993, 34, 951

l- WSiMq

, SnC14

CH2C12,O°C,30 min 2.TBAF,m

(1.

.

Hioki. H,; Okauda,M.; Miyagi, W.; It& S. Tetrahedron Lett., 1993, 34, 6131

1.1) 74%

253

Alcohol – Amine

Section 326

Keck. G&, PaIani, A. Tetrahedrdn Lett., 1993, 34, 3223 H

4r H

5 eq. TABH , AcOH/MeCN Me

Me

P

-35OC +

P &

+22”C

* NHOBn TABH = Me+JH BH(OAc)3 Osterhout, M.H.; Reddy, J.P. Tetrahedron Lett., 1993, 34, 3271 N-OBn

DA;

Ph-

Br

2 eq. SmI2, THF-HMPA CHO t N=C , -15OC, 3h

91%

Murakami, M.; Kawano, T.; Ito, H.; Ito. Y, J. Org. Chem., 1993, 58, 1458

0

H 1. LDA 2. PhCHO

+

Ph

*

mn2

Lagu, B.R.; Crane, H.M.; m.

*

NBn2

(80:20, R)

D.C, J. Org. Chem., 1993, 58, 4191 EtzNzCu(CN)Liz , THF

0 -78OC + rt

N. Y,; Asao, N.; Meguro, M.; Tsukuda, N.; Nemoto, H.; Sadayori, N.; Wilson, J.G.; Nakamura, H. .I. Chem. Sot. Chem. Commun., 1993, 1201

254

Compendium of Organic Synthetic Methods, Vo19

Section 326

Yb(OTf)3, NHEt2 CH&

C6H13

97%

,20 min mt2

w-h3

> 99% a-attack Chini, M.; Crotti, P.; Favero, L.; Macchia, F.; Pineschi, M. Tetruhedrun Lett., 1994, 35,433 C8H

7

Et2NH , LiBF4, MeCN 80°C , 18h

* c8H1ym.YOH Chini, M.; Crotti. P,; Favero, L.; Macchia, F. Tetrahedron Lett., 1994, 35, 761 b

CbZ

0

CbZ

79) 52%

.

(21

&&,Q. T,; Tajiri, IS.; Harimoto, T.; Ninomiya, I.; Kiguchi, T. Tetrahedron Lett., 1994, X5,2205 H

H CH3N02 ,2 eq. AlC13 w 8O”C, 5h

/““” 70%

/

.

Sarton,;

Bigi, F.; Maggi, R.; Tomasini, F. Tetrahedron Lett., 1994, 35, 2393 Ph I N /

1. Li, cat. cl(jf&j 2. PhCHO *

3. H20

Almena, J.; Foubelo, F.; Yus. MJ.

0 o=

68%

PhHN-Ph

various electrophiles were used Org. Chem., 1994, 59, 3210 93% (1:l)

MeCH=N-OMe , iPrOH

sono.

& /

* e’

NHOMe

T,; Kise, N.; Fujimoto, T.; Yamanami, A.; Nomura, R. J. Org. Chem., 1994, 59, 1730

Section 326

Alcohol – Amine

c”, f”’

1. BH#Me2,

255

c’)

THF

J

w

2. MeOH

45%

3. H202, NaOH w-h1

C&9

Goralski. CT%;Hasha,D.L.; Nicholson, L.W.; Zakett, D.; Fisher, G.B.; Singaram. B, Tetrahedron L&t., 1994, 35, 3251 0

A

2

H

Sm , Me$iCl/NaI , MeCN rt, 15min

P

9

/

OH

Phq-p 72%

Akane, N.; Hatano, T.; Kusui, H.; Nishiyama, Y .; Ishii. Y cJ. Org. Chem., 1994, 59, 7902

NBn2

mn2

(92:8 RS)

90%

with LDA

(63:7 R:S) 90% Lagu, B.R.; Liotta. DC, Tetrahedron Lett., 1994, 35,4485

l.BMS,THF

J5 ~c.T.;

.

3. H202, NaOH

Hasha,D.L.; Nicholson, L.W.; Sine.

R, Tetrahedron Lett., 1994, 35, 5165

OH ultrasound,Al(Hg) , aq. THF 2h iJo Fitch, R.W.; Luzzio. F.A, Tetrahedron Lett., 1994, 35, 6013

92% NH2

Section 326

Compendiumof Organic Synthetic Methods, Vol9

256

t-BuNH2 , CH2C12 5% Yb(OTf)3, rt ,16h c8H~~mt-Bi8H~~;Bu m

99 P,; Favero, L.; Macchia, F.; Pineschi, M. Tetrahedron Lejt., 1994, 35, 7089 Bn I

Bn I

1. Cp$Zr(Bu);!, THF -78OC+ rt ,4h OMe

2. BF3aEt2, THF , O°C 3. aq. NaOH

82% (>98:2 syn:anti)

Ito, H.; Ikeuchi, Y.; Taeuchi. T,; Hanzawa, Y.; Shiro, M. J. Am. Chem. Sot., 1994, 116, 5469 Na,iPrOH,THF

76% (erythro/threo = 0.8)

Bartoli, G.; Cimarelli, C.; Palmieri. G, J. Chem. Sot., Perkin Trans. I., 1994, 537

A

, SmI2

Q+ ‘0I /

*

THP , HMPA

85%

Booth, SE.; Benneche,T.; Undheim. K, Tetrahedron, 1995, 51, 3665 Ph 0

NHPh

PhNH2 , TiC13, PhCHO THF/CH$12, Py , rt *

M-+

Clerici, A.; Clerici, L.; porta 0, Tetrahedron L&t., 1995, 36, 5955

9 % HO Ph

Ph 76%

Section 327

Alcohol – Ester

257

OH

BnNH2,lOkbar ,CH2C12

90% cat. Yb(OTf), , rt ,6d Meguro, M.; Asao, N.; mote.

030s=Nt-Bu , DME ,25OC Phw

Ph

NHBn

Y, J. Chem. Sot., Perkin Trans. I., 1994, 2597

quinuclidine , 36h

NH?-Bu

– Ph+ph

+ Phqph OH

OH

..

(97

3)

Rubinstein, H.; Svendsen,J.S. Acta Chem. Stand. B., 1994, 48, 439 1. TFAA, CHg12 rt ,4h OH

2. K2CO3

95%

Fontenas,C.; Bejan, E.; Haddon, H.A.; Belavoine, G.G.A,Synth. Commun., 1995,25, 629

SECTION 327: ALCOHOL, OBn = =

THIOL – ESTER

t

=

CHO

CO2Me

3% LiC104, -30°C CHg12, 4h

OSiMe2cBu

..

(92 Reetz. M.T,; Fox, D.N.A. Tetrahedron Lett., 1993, 34, 1119

8)

>84%

EtOH , CO, NaBr , iPr2NEt

-I.;

Pd2(C4H7)& , maleic anhydride ‘) H*co2Et Maruyama, T.; Makuta, T.; Yamamoto. A. Tetrahedron Lett., 1993, 34, iI35

w

Me

PhCHO ,5% SmI2,5 min

Ph

CH2C12, -78OC -$< OTMS Van de Weghe, P.; Collin, J, Tetrahedron Lett., 1993, 34, 3881

C02Me OTMS

95%

258

Compendiumof Organic Synthetic Methods, Vol9

/L

OH

Yeast, pet. ether, H20 C02Et

Section 327

*

rt, Id

AC02Et

58% (94%ee) Yeast = Saccharomyces cerevisiae Jayasinghe,L.Y.; Smallridge. A.J,; Trewhella, M.A. Tetrahedron L&t., 1993, 34, 3949 0

0

C02Me Mn(OAc)[email protected]

OH

+

A

Cu(OAc)pHzO

9%

78%

25OC

ix

-OH

OMe

Oshima, T.; Sodeoka,M.; Shibasaki,M. Tetrahedron L&t., 1993, 34, 8509 . ;co2Me

NHC02t-Bu

t-Buo2cJ

c

*

-t &Me$‘h w.

‘.~~ao~~;a~ 2.5% aq. HCl

0 i bH

0

J&; Zhang, J. J. Org. Chem., 1993, 58, 294 OSiMe3 I PhCHO

Ph

m12

C02Me

er. LB, .I. Org. Chem., 1993, 58, 2324 TMs

A

OMe

92%

p-MS

10% [Cp2Zr(Ot-Bu)THF][BPh4]

:=

C02Me

PTMS +

&CO$Ie I= Z s=

CH2C12, PhCHO , rt , lh -^(

..

(1.1

1)

95%

Hong, Y .; Norris, D.J.; Collins, S, J. Org. Chem., 1993, 58, 3591 1. LDA 2. Et2AlC1

OH

/COzt-Bu *

56%

xx 2’ (84:16 syn:anti) m. S&; Fried, J.A.; Grassl, Y.N.; Marolewski, A.E.; Pelton, E.A.; Poel, T.-J.; Rezanka, D.S.; Whittaker, M.R. J. Org. Chem., 1993, 58, 7304 3* ‘s

Section 327

Alcohol – Ester

259

BrCH2C02Et, PhTeLiKeC13 C02Et ether, OOC +

rt 95%

Fukuzawa. S.-i; Hirai, K. J. Chem. Sot., Perkin Trans. I., 1993, 1963 oxido reductase from Geotrichum candidum

C02Et

QH 0 = E

C02Et

500 mM bis-TRIS-HCl 24h , NaDPH , ADH , glucose

93%

(>99% de; 92% ee) Kawai. Y,; Takanobe, K.; Tsujimoto, M.; Ohno, A. Tetrahedron Lett., 1994, 35, 147 PhCHO

+

I-(,, TBSO

~e/wI-MP ()pMp

CH2C12, -78’C

+ OTBS (6

PMP = p-methoxyphenyl

UOPMP &TBS 94) 95% 92%ee

..

Kobayashi. S,; Kawasuji, T. Tetrahedron Lett., 1994, 35, 3329 OH 3 eq. CH2=CHC02Me

COzMe

1.2 MgBr2 , CH2C12 O°C , lh 58% (> 20~1 endo:exo) Woo. SH, Tetrahedron Lett., 1994, 35, 3975 TMS

+

ooka. S,; Kido, Y.; Kaneko, Y. Tetrahedron Lett., 1994, 35, 5243

260

Compendium of Organic Synthetic Methods, Vo19

BnOCH$HO

Section 327

,5% binolTiC12

toluene , O°C ,2h . -K.;

81% (94% ee, R)

.

Matsukawa, S. J. Am. Chem. Sot., 1994, 116, 4077 0

CaMe

MeOH , Amberlyst-15 ,2Oh

96% 0 bd.

OH

* c c R.c; Selvapalam, N. Synth. Commun., 1994, 24, 2743 OHC I

I–

1

CO2iR

L = chiral imine ligand Hayashi, M.; Inoue, T.; C)euni. N, .I. Chem. Sot. Chem. Commun., 1994, 341

o=

Br/co2Et

, THF ,2h

0

LVT, rt

*

(-pco2Et

LVT = low valent titanium 67% Aoyagi, Y.; Tanaka, W.; Ohta. A, J. Chem. Sot. Chem. Commun., 1994, 1225 1. BuLi , ether, -4OOC 2. PhCHO

2”

H w

P

3.03 , CH2C12, -78°C 4. Me$

Ph*CO

2 Me

51% Hormuth, S.; &i&&

H.-U.; Dorsch, D. Liebigs Ann. Chem., 1994, 121 RuBr&hiral

C02Me

mM.J.;

bis-phosphine)

60 psi H2 , aq. MeOH

*

OH = = z &COzMe

quant. (99% ee, S) Harper, T.G.P.; Kalberg, C.S. J. Am. Chem. Sot., 1995, 117, 4423

Section 328

Alcohol – Ether

261

0

VO(OAC)~ , PhH , TBHP –

A Ph

o//O” 98%

Choudary, B.M.; Reddy, P.N. Synlett, 1995,959 Also via:

Section 313 (Alcohol – Carboxylic Acid).

SECTION 328:

ALCOHOL, THIOL – ETHER, EPOXIDE, THIOETHER

E+Z

. 1) (18 Mandai. T,; Ueda, M.; Kashiwagi, K.; Kawada, M. Tetrahedron Lett.: 1993, 34, 111

0 0

Uozumi, Y.; w.

1. 0.1% [PdC1(rtC3H5)]2 0.2% R-MOP, HSiCl3

H RMOP b 65 x 83%

(g5% ee) T, Tetrahedron Lett., 1993, 34, 2335

1. BH#Me2, Me2S , O°C 2. aq. NaOH , Hz02 3. NaOH

mder.

=3 .

OMe

40°C, 24h 2. KF , KHC03, Hz02

78%

G,&; Bobbitt, K.L.t .I. Am. Chem. Sot., 1993, 11.5, 7517

pm2

Section 328

Compendium of Organic Synthetic Methods, Vol9

262

1. BuCHO , Li(powder) 5% DTBB , THF, O°C 2 H o

EtQc1

l

H Et

*

2

gK

87%

Bu

Guijarro, A.; yuS. n& Tetrahedron Lett., 1993, 34, 3487

‘-“’

cat BF3 OEt2 .

42%

l

Mark& I.E.; Bayston, D.J. Tetrahedron Lett., 1993, 34, 6595

phxph

n

2 eq. BHpSMe2 2 eq. TMSOTf

Bartels, B.; Hunter. R, J. Org. Chem., 1993, 58, 6756

7 PhSH , SiO2

;;;p

+ z&SPh

t

20°C, 20h

Me3Si

CdJ

13

89% Raubo, P.; w

C&

13

14%

a-h3

J, Synlett, 1993, 25 ClCH2SPh , SmI2 t

0

(-KS,,

o=

73% Yamashita, M.; Kitagawa, K.; Ohhara, T.; Iida, Y.; Masumi, A.; Kawasaki, I.; Ohta. S, Chem. Lett., 1993, 653

R

1. PhONa , DMF

A0

)

PhOTOBn

2. HCl-H20 k/

OBn

Cwlsen. P.H.J*; Aase, K. Acta Chem. Stand. B., 1993, 47, 617

OH 81%

Section 328

Alcohol – Ether

263

cat. FeC13, MeOH ,25OC

Ph

OH

0.75h

90%

N,; Salehi, P. Synthesis, 1994, 1152

a

OH eq. eq. CH2C12, 12h , rt –

2. HOONa 1.3

c

Re207 ,9

0

2,6-lutidine

OF

78%

OH

0

Boyce, R.S.; Kennedy, R.M. Tetrahedron Left., 1994, 35, 5133

1. SO(Im)2 OH 2. PhO- Li+

OH

34% OH D, Tetrahedron Lett., 1994, 35, 6279

El Arabi Aouad, M.; El Meslouti, A.; Uzan, R.; mere. OH

OH PhthNSCl , CHC13 , 60°C, 4d

SNPhth

64%

Me0

precursor to o-thioquinones Capozzi, G.; Menichetti. S,: Nativi. C,; Simonti, M.C. Tetrahedron Lett., 1994, 35, 9451

v H

Marson.;

HgO , dil. H2SO4 , 20°C Wll

0

Wll

-*

OH 73% Harper, S.; Wrigglesworth, R. J. Chem. Sot. Chem. Commun., 1994, 1879

1. t-BuLi , THF , -78OC 2. cyclohexanone ~T,.A,;

*

S

HO Dullweber, U.; Branan, B.M. Heterocycles, 1994, 37, 187

75%

264

Compendiumof Organic Synthetic Methods, Vo19

1. Bu$nCH(OEt)z, BuLi THF , -78OC

PhCHO

Section 328

Ph

CH(OEt)z

c

I

2. aq. NH4Cl

OH 65% Parrain, J.-L.; Beaudet,I.; Cintrat, J.-C.; Duch$ne, A.; Quintard. J.-P,Bull. Sot. Chim. FL, 1994, 131, 304

(CFcO2)Re03 , O°C 2,6-lutidine , CH2C12

McDonald. FL; Towne, T.B. J. Org. Chem., 1995, 60, 5750

-OH

PhSeCl , CHCl3 –

LO,

= = XePh

W Cooper, M.A.; Ward. A.D, Tetrahedron Let?., 1995, 36, 2327

+

L,, ..

= = bH 36) quant.

OH OH

88%

2.H20

Corey. EL; Palani, A. Tetrahedron Let?., 1995, 36, 3485

S

J&l.

S,; Cho, C.M. Tetrahedron Let?., 1995, 36, 4845

HO

Section 329

(3-I

1

265

Alcohol – Halide

0

1.2% Cp2Ti(O4ClC&& , toluene 1% TBAF , Al2O3,5 PMHS , rt

w-h

0

OH

2.1M NaOH , TI-IF

* u PMHS = polymethylhydrosiloxane 94% (70:1) SLJ. Am. Chem. Sot., 1995, 117, 12641 Verdagauer,X.; Berk, S.C.; md. 0

BF3GEt2, NaBH3CN 6h .

0IOH 87%

.

Stlkrrshna. &, Viswajanani, R. Tetrahedron, 1995, SI, 3339 OMe

e’ , MeOH, aq. MeCN , Bu&IClO4 lh

OH 96%

Safavi. A.: Iranpoor. NJ Fotuhi, L. Bull. Chem. Sot. Jpn., 1995, 68, 259 1 REVIEW:

“Metal-Catalyzed Direct Hydroxy-Epoxidation of Olefins,” Adam. W,; Richter, M.J. Accts. Chem. Res., 1994, 27, 57

SECTION 329: ALCOHOL,

THIOL – HALIDE, SULFONATE

1. LDA. ZnCl2 , THF . -78OC mcl

2. PhCHO

80%

Cl Mallaiah, IS.; Satyanarayana,J.; Ila H,; Junjappa,H. Tetrahedron L&t., 1993, 34, 3145

a; 58,486

.

. 77) 74% (23 Furutani, H.; Ansari, M.H.; Sakai, T.; Utaka, M.; Takeda, A. J. Org. Chem., 1993,

266

Compendiumof Organic Synthetic Methods, Vo19

Section 329

1. DibaI , CHg12, -78OC [email protected]

83%

2.ZnBr2, BussF CHzCl2, 40°C T,; Hayashi, H.; Yamanaka, H. Tetrahedron Lett., 1993, 34, 5777

. ma.

MgBr2, Bu$IBH4 –

ether/CHglz:

72%

‘-Ph +

.Ph 22% “Ph Bailey, P.L.; Briggs, A.D.; Jackson,R.F.W.; Pietruszka,J. Tetrahedron Mt., 1993, 34, 6611 Mg(NO& , Bu4NBr ,5h CHC13

OH

Y.-Q, Koo, B.-A.; Ko, J.-A.; Cho, Y.-S. Chem. Lett., 1993, 1907

93%

NaI04, NaHS03

k

Masuda, H.; Takase,K.; Nishio, M.; Hasegawa,A.; Nishiyama, Y.; Ishii. Y, J. Org. Chem., 1994, 59, 5550 Lick , DMF , 70°C , Id

Ph

-,jPhJ/H (35

+Lc1 ..

65)

Nymann, K.; Svendsen,J.S. Acta Chem. Stand. B., 1994, 48, I83 Br

PhCHO

OH CN

9 In

CN

84% (56:44 erythro:threo)

Araki, S.; Yamada, M.; Butsugan. Y, BUZZ.Chem. Sot. Jpn., 1994, 67, 1126

90%

Section 330

Alcohol – Ketone

267

REVIEW:

“Regioselectiveanbd ChemoselectiveSynthesisof Halohydrins by Cleavageof Oxiranes with Metal Halides,” m. C,; Righi, G. Synthesis, 1994, 225 SECTION

330: ALCOHOL,

THIOL

– KETONE

Rawal. VH,; Krishnamurthy, V.; Fabre,A. Tetrahedron Lett., 1993, 34, 2899 M F3

3

P 0

,,

15 min 96% Curci, R.; D’Accolti, L.; Detomaso,A.; Fusco, C.; Takeuchi. K.; Ohga, Y.; Eaton.& Tetrahedron Lett., 1993, 34,4559 TIPS

P

PhCHO , Me& rps

w

p”

88%

WPh Shoda,H.; Nakamura,T.; Tanino, K.; Kuwajima, I Tetrahedron Lett., 1993, 34, 6281

1. Me$i(OTf)Z , NEt3 m &

I

2. PhCHO ; Nishio, K. .I. Org. Chem., 1993, 58, 2647

HO*

78%

(919

syn:anti)

Ph OAc

OAc RuC13,MeCO# MeCN – Hz0 – CH2C12

78%

Murahashl. S.-I,; Saito, T.; Hanaoka,H.; Murakami, Y.; Naota, T.; Kumobayashi, H.; Akutagawa, S. J. Org. Chem., 1993, 58, 2929

Compendium of Organic Synthetic Methods, Vol9

xc

Section 330

H

0 0

’ acetone >96%

o”c

OH

OH (>98% ee , R)

D’Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci. R, J. Org. C&m., 1993, 58, 3600

0 II

1. BuLi , CO, -1lOOC THF/pentane/ether 2. rt , H30+ Hui, R.C.; Wang, W.-L. J. Org. Chem., 1993, 58, 5843

Sevferth.;

H PhCHO ,5% Sc(OTf)3, aq. THF *

Ph Y 83%

,; Hachiya, I.; Ishitani, H.; Araki, M. Synlett, 1993,472

Ph

PhCHO 2%

0

9 CH2C12

*

W&)3

PhU

Ph 84%

Ishihara, K.; Hananki, N.; Yamamoto. HJynlett,

1993, 577

0 PhwcHo

+

HMPA,rt,THF

, SmI

2 *

Ph*

0 83% (83:17 antixyn)

Miyoshi, N.; Takeuchi, S.; Ohgo, Y. Chem. Lett., 1993, 959 –

MeC03H , cat. OsC13

Phv0I-I

Phv

MeCN-H20-CH2Q . Murahashl. S.-L; Naota, T.; Hanaoka, H. Chem. Lett., 1993, 1767

0

62%

269

Alcohol – Ketone

Section 330

PhCHO , A1203 ultrasound, 22h

..

(77 Ranu, Ike,

23) 75%

Chakraborty, R. Tetrahedron, 1993,49, 5333

PhCH2CH0 CHO

)

Phk

+

Ph;

H20, SmI2 OH

?)H

.

(39

61) 64%

Miyoshi, N.; Takeuchi, S.; Ohgo, Y. Chem. Lett., 1993, 2129

1.

==c

PhCHO

Bu

, EtCN , -78OC

20% chid acyloxyborane 2. aq. HCl

*

0

= =

Bu

Pha

81% (85% ee, R) Ishihara, K.; Maruyama, T.; Mouri, M.; Gao, Q.; Furuta, K.; Yamamoto. H, Bull. Chem. SOC. Jpn., 1993, 66, 3483

c

1

1. 2.2 eq. SmI3 , tetrahydropyran 2. propanal 3. H30+

0

H

c

0

95%

955

(trans:cis)

J.-L; Colomb, M.; Kagan, H.& Tetrahedron L&t., 1994, 35, 1723

OH

TFA , CDC13 ) 2d

ph 0

Dmhoux.;

Doris.

Tetrahedron Lett., 1994, 35, 2017

270

Compendium of Organic Synthetic Methods, Vol9

a Ph

Section 330

Cl

86%

3 eq. pyridine

C02Me

Araneo, S.; Clerici, A.; Porta. 0, Tetrahedron Lett., 1994, 35, 2213

P hl

OH

p)-(=)-oH

Cl

cat. HZSM-5 DCE , reflux

67%

HZSM-5 = acidic zeolite [SiO$A1203 = 401 Paul, V.; Sudalai, A.; Daniel, T.; Srinivasan.V, Tetrahedron Lett., 1994, 35, 2601 0

1. LDA , THF , -78OC 2. (iPrO)$Cl 3. acetone ,

>

8

II Ph 7

, -78OC

OH 5 1% conversion (88% yield)

4. aq. NH8

a.

W,; Mtiller, M.; Prechtl, F. J. Org. Chem., 1994, 59, 2358 OH

0

PhCHO , 10% Sm(hmds)J -30°C) 18h

Sasai, H.; Arai, S.; Shibasaki. M, J. Org. Chem., 1994,

UI -“iMe

VS.;

.

PhCHO , Yb(OTf)3

OH

aq. THF, rt , 19h

Hachiya, I. J. Org. Chem., 1994, 59, 3590

Ph 9 1% (73:27 syn:anti)

271

Alcohol – Ketone

Section 330

1. Me3A1, PhSeH 2. Me$=CHCH2CHO

92%x62%

w

3. BusnH, hv

I.-Y.C,; Lee, J.H.; Lee, H.W. Tetrahedron Lett., 1994, 35, 4173 OH

0

l.NaHMDS,THF * 2. PhCHO

Ph

Ph

+

.

(94

6)

69%

Goh, J.B.; Lagu, B.R.; Wurster, J.; J,iom. DC, Tetrahedron Lett:, 1994, 35, 6029 H 0

1, LHMDS , toluene-hexane t-Bu

2. Y(OTfl3,

HIIIIII –

OOC, 18h

t-Bu

x,

99% 0 crou. P,; Di Bussolo, V.; Favero, L.; Macchia, F.; Pineschi, M. Tetrahedron Lett., 1994, 35, 6537 i FfKfR-BINAPI

Ph-

, PhC12SiSiMe3,PhH Ph* w

0

l

3+

4. HBF4 5. H202 Matsumoto, Y.; Hayashi. T,: Ito, Y. Tetrahedron, 1994, SO, 335

OH

0

73~78%

, Yb(OTf-)3, 0°C 0

PhCHO

Ph

iPrmt , ether, 3h

92% (34:66 threo:erythro)

Fukuzawa. S.-i,; Tsuchimoto, T.; Kanai, T.. Bull. Chem. Sot. Jpn., 1994, 67, 2227

Compendiumof Organic Synthetic Methods, Vol9

272

Jr

Ph

Section 330

OTMS OzMe -=c Me

BuflClOd , e’

SnBu3

*

Ph=

Yoshida. L; Morita, Y.; Ishichi, Y.; Ime. S, Tetrahedron Lett., 1994, 35, 5247

dPh

Enbolm.;

Sm1z2Br

94%

f”fPh

Schreier, J.A. J. Org. Chem., 1995, 60, 1110 PhCHO , MS 4A, 13h 5% PdClz[R-DINAPI-AgOTf *

23°C

Phu;

+

Phufi

87%

9%

Sodeoka,M.; Ohrai, IS.; Shibasaki. m J. Org. Chem.,1995, 60, 2648

‘: 0

, acetone, IX, ld 92%

OH 0 Bovicelli. Pa;Lupattelli, P.; Sanetti, A.; Mincione, E. Tetrahedron Lett., 1995, 36, 3031

OHC Zn(NO3)2, acetoneHo Me2NCH2CH20H 30°C ,6h

pH 10.1 pH 11.0

98% 0%

Buonom. ET,; Rosauer,KG.; Dai, L. Tetrahedron Lett., 1995, 36,4o$I

0% 100%

Section 330

Alcohol – Ketone

273

H

K

1. Bu$nH , AIBN, PhH relux

0 –

Ph

2. PhCHO, 10°C, 12h

I

ti

73% (61 erytrho:threo) Enholm. EJ,; WhitIey, P.E. Tetrahedron Lett., 1995, 36, 9157

0

1. SmI2 Br

,

M%5 4

0

2. Hz0

OH

Ph Y

*

77% O Arime, T.; Takahashi, H.; Kobayashi, S.; Yamaguchi, S.; Mot-i. N, Synth. Commun., 1995, 25, 389 DMSO , KSF , microwave, 3 min Ph / . . lllemrn

0

OH 0

55%

DJ Hammadi, M. Synth. Commun., 1995, 25, 3141 0

Sm.

Ph *

1. LDA 2. Ti(OiPr)$l

53%

3. TBHP, BaO 4. NH8 , Hfl m; Kluge, R.; SchiiBer, M.; Hoffmann, G. Tetrahedron, 1995, 51, 3175 OH

$ A (CH2)7

Cl3CCO2H , 11°C , Cl2 , MeOH wh9

EtOH, NaHC03

0 w

r

98%

k (CH2)7

CgHW

Tassirznon. P.S.&; De Wit, D.; De Rijk, T.C.; De Buyck, L.F. Tetrahedron, 1995, 51, 11863

Br-COzEt

1.2 q. SmI2, -6OOC –+ -5O.C * 2. cyclohexanone , -50°C -+ 0°C

cC02Et OH

Utimoto. &; Matsui, T.; Takai, T.; Matsubara, S. Chem. Lett., 1995, 197

98%

274

Section 33 1

Compendium of Organic Synthetic Methods, Vo19

1. AlMe I Ph Aoki, Y.; ‘cr

Ph 79% (13:87 erythro:threo)

2. PhCHO i

I(.: Uti moto. K, Chem. L&t., 1995,463

Ph

PhCHO

-78OC ,6.5h Ishihara, K.; Hanaki, N.; Funawashi, M.; Miyata,M.; Yamamoto. 1995, 68, 1721

SECTION 331: ALCOHOL,

THIOL

Ph Bull. Chem. Sot. Jpn.,

– NITRILE

3: 1 EtCN-CH2C12, 1Oh 20% Mg-dihydrooxazolidine

c&3-cHo Corev.EJ.; ww,

OMS catalyst E * ca13>cN 12% bis-dihydro oxazolidine derivative z. Tetrahedron Lett., 1993, 34, 4001 H

4

CN

92h9* 100 units enzyme O.lM citrate buffer

NCHO

)

acN

93%Jz;Fon

enzyme = hydroxynitrile lyase from Hevea brasiliensis Klempier, N.; Ga; Hayn, M. Tetrahedron Lett., 1993, 34, 4769

80% Ohno, H.; Mori, A.; m. 02

88% (95%=, 9

S, Chem. Lett., 1993, 975 1. LiCH2CN 2. H30+ *

[email protected]%

;fIaye. TJL; Crawford, K.B. J. Org. Chem., 1994, 59, 520

Section 33 1

Alcohol – Nitrile

0

275

1. TMSCN , CH2C12 , rt KCN/18-crown-6

0

2. MeOH/THF , SmI2

H”-(=)-cN 80%

Olson, S.H.; Danishefskv. SL Tetrahedron Lett., 1994, 35, 7901 OH 5

1. LDA , THF , -78OC

OH CN

ph-CN 2. PhCHO

*

Ph T

CN +

Ph hc

Ph Ph . 1) 70% (5 5 Carlier. P.R; Lo, KM.; Lo, M.M.-C.; Williams, I.D: J. Org. C’hem.,‘1995, 60, 7511 OH [ LDA , PhCH2CN ] , TMSCl

CN

PhCHO

97%

Zhou, J.J.P.; Zhong, B.; mennan.

Ph Rh J. Org. Chem., 1995, 60, 2261 HO

*

PhCHO Me$iCN

, Ti(OiPr)d 72% (91% ee, S)

Balm. C,; Miiller, P. Tetrahedron Lett., 1995, 36, 1625

GoI~~~-~H~ tm;

Cl Cl Zhmg, X.-L.; Han, Y .; Tao, W.-T.; Huann. Y .-2, J. Chem. Sot., Perkin Trans. l., 199% 189 Review:

“Catalytic Asymmetric Cyanohydrin Synthesis,” North. M, Synlett, 1993, 807

276

Section 332

Compendium of Organic Synthetic Methods, Vo19

SECTION 332: ALCOHOL,

THIOL – ALKENE

Allylic and benzylic hydroxylation (C=C-C-H -+ C=C-C-OH, etc.) is listed in Section 41 (Alcohols from Hydrides).

2 MeMgBr , CuCN BF3QEt2, THF

Bn

Bn -78OC

OH E z=

Me

=

88%

S-L; Lee, D-H.; Sim, H-S.; Lim, J-S. Tetrahedron Lett., 1993, 34,91 1. TIPSCl 2. MeLi -L PhCHO

0

.

JNEt2 yJ+L–yw

yj&

L 81%

Tsukazaki, M.; Snieckus. V, Tetrahedron Lett., 1993, 34,411 Lee, J.; Tsukazaki, M.; Snieckus, V, Tetrahedron Left., 1993, 34, 415 2SmI2,r-t 2 t-BuOH , THF

Me0

Me0

Me0

5 +

CHO 7r

I

(2 OH

.

..

3

OH

1) 66%

Glllmann. T, Tetrahedron Lett., 1993, 34, 607

SPh

BuLi , THF , -78OC t

C5Hll

OH Takano. S,; Sugihara, Y.; Ogasawara, K. Tetrahedron Lett., 1993, 34 845

5% DTBB , THF, O°C

i

I

only product (90%)

OH

D.&; Kim, K.; Martinez, J.P. Tetrahedron Lett., 1993, 34, 3071 1. PhCHO , DMF , 0°C wSC13

y

., OH = = Q = = = t.

2

97)

Kobavashi. S,; Nishio, K. Tetrahedron L&t., 1993, 34, 3453

10 eq. BuLi , 10 min )

89%

71%

OH

Bu

Lautens. M,; Gajda, C. Tetrahedron Lett., 1993, 34, 4591 BI-j

B

/-Br

rJ

C&CHO

, EG-Zn e

DMF , O°C ,2h

C3H3

72% EG-Zn = electrogenerated reactive zinc Tokuda. M,; Mimura, N.; Karasawa, T.; Fujita, H.; winome. 7607

H, Tetrahedron L&t., 1993, 34,

PhCHO , hv (>320 nm) EtCN , -78°C ,5h E-snBu3

A+&

+ EthPh (30

muwa.

..

k; Shiigi, J.; Nishigaichi, Y. Tetrahedron Mt., 1993, 34, 3457

70) (86: 14 E.z)

278

Compendium of Organic Synthetic Methods, Vo19

Section 332

Et2Zn , Ti(OiPr)d , 12h -6OOC + -55OC

d

8%

,Ti(OiPrb

(93% ee)

Y

Rozema, M.J.; Eisenberg, C.; Liitjens, H.; Ostwald, R.; Belyk, K.; wel. LAt., 1993, 34, 3115

4

P, Tetrahedron

1,2dichlorobenzene , 12h reflux , CO.5torr

llllI~lll

t

Q

=

90%

bH

*

OH Janardhanam, S.; Devan, B.; RaiogoDalan. K, Tetrahedron L&t., 1993, 34,676l 1. Sharpless epoxidation 2. TsCl

Ph OH

78% (>90% ee)

3. Te , LiBHEt3 , THF TBAF,lt

* – D-c; Discordia, R.P.; Zhang, Y.; Murphy, C.K.; Kumar, A.; Pepito, A.S.; Wang, Y. J. Org. Chem., 1993, 58, 718 Bu

iPrMgBr , THF Bu

wJP)2Ni2c12

Ducoux, J.-P.; LeMenez, P.; tine&

Bu *

+

h

(CH2)2CH20H

w

u-mCH20H (>25 1) 60 N… Wenkert. E, J. Org: Chem., 1993, 58, 1290

MeJSiSnBu3 , DMF 86%

CsF, rt, lh *b mu;

OH Isono, N.; Kaneta, N.; Shibasaki, M. J. Org. Chem., 1993, 58, 2972

Section 332

Alcohol – Alkene

279

OH w

hv,CO,THF,8h

c. CA;

75

Xu, D.; Gladstone, B.G. J. Org. Chem., 1993, 58, 538

0

EtMgBr , 10% Zr complex THF ,25*C

0

Morken, J.P.; Didiuk, M.T.; Hove-

OTMS

65% (>97% ee) A.H, J. Am. Chem. Sot., 1993, 115, 6997

5% (binol)TiClz , BnOg-CHO C02Bn Me

63% (99:l syn:anti; 99:l ZE; 99% ee, R) Mikami. K.; Matsukawa, S. J. Am. Chem. Sot., 1993, 115, 7039

‘* –cbv

SiMe3 ’ “:‘igchiral ligmd

phu

*

PhCHO

Z = = 63% (92% ee)(96:4 erythro:threo) bH Ishihara, K.; Mouri, M.; Gao, Q.; Maruyama, T.; Furuta, K.; Yamamoto, H,J. Am. Chem. sot., 1993, 115, 11490 2. TBAF

OH –i=h’

, 10% Pd(OAc)z

2 Na02CH ,2 BuflCl ,2 iPr2NEt MezNCOMe ,8O*C, Id ~R.c.;

Ding, S.; Tu, C. Synlett, 1993, 145

70% (5644 E.-z)

280

Compendium of Organic Synthetic Methods, Vo19

Section 332

x= Sin&ton.

D.A,; Redman, A.M. Tetrahedron Lett., 1994, 35, 509

&,gmak. J.D,; Geng, B.; Uang, S.; Strickland, J.B. Tetrahedron Lett., 1994, 35, 985 1. Cp$Zr(H)Cl , CH$12 2. Me2Zn

Bum

3. PhCHO , O°C

Bu 94%

WiDf. P,; Xu, W. Tetrahedron Lett., 1994, 35, 5197 //oO

2eq. Me#=CH2

,THF

*

z

-1OOC + rt 80% OH Alcaraz, L.; Hamett, J.J.; Mioskowski, C.; Martel, J.P.; Le Gall, T.; Shin, D.-S.; Falck, J.R. Tetrahedron Lett., 1994, 35, 5449

0 /

/

1. ($-C$-I,hTiCl

iPrMgC.1, THF , -50°C 2. PhCHO , -50°C +

= -20°C

@Ph+

@Ph (1.44

:

1) 42%

Szymoniak, J.; Felix, D.; Moi’se. C, Tetrahedron Lett., 1994, 35, 8613

1. HSiC13 , cat. Pd(PPh& 2* Phw

CHo , DMF

Kobavashl, . S .; Nishio, K. Synthesis, 1994, 457

Ph 87% (>99: 1 syn:anti)

Section 332

Alcohol – AIkene

phCN,Nyluene9

281

refhx, 3hwfiMe 73% Ph

(3:2 synxnti)

Kim. S,; Cho, C.M. Tetrahedron Lett., 1994, 35, 8405

Pd(OAc)z ,3 PPh3 , PhH 7O*C, 16h

CHO

-5

OH 47% Watanabe, T.; Sakai, M.; Miyaura, N.; Suzuki, A,.!. Chem. Sot. Chem. Commun., 1994,467 OH

BuMgBr N-NHTs

* .,,t5L Takhi, M.; Yadav, J.S. Tetrahedron Lett., 1995, 36, 307

Chandrasekhar.,

1. Li , NH3 , THF-EtOH 2. TBAF , THF

Bu

, -78OC

* ,, ,*’ *

3.30% aq. H202, KHCO3 , MeOH OH Taber. D.F*; Yet, L.; Bhamidipati, R.S. Tetrahedron Lett., 1995, 36, 351

5% Pdz(dba)3*CHC13 , THF 20% PPh3 , heat MpM(,o

OH

93% KanG S-K,; Park, D.-C.; Park, C.-H.; Hong, R.-K. Tetrahedron Lett., 1995, 36, 405 Phs

1. Cp2TiClz/2 BuLi , 0°C 2-

ma.

PW

CHO

T,; Miura, I.; Horikawa, Y.; Fujiwara, T. Tetrahedron Lett., 1995, 36, 1495

282

Compendiumof Organic Synthetic Methods, Vol9

Section 332

Co(tdcpp) = [5,10,15,20-tetrakis(2,6-dichlorophenyl) porphinato] Cobalt (II) -Y.; Sugamoto, K.; Nakama, T.; Sakamoto, T.; Matsui, T.; Nakayama, M. Tetrahedron Lett., 1995, 36, 18’79 Ph

Ph 3 t-BuOK, BuLi THF , -78OC

OH *

R=TBS (79 R=H (20 Tomooka, K.; Keong, P.-H.; Nakai. T, Tetrahedron L&t., 1995, 36,

.. .

21) 48% 80) 90%

&89

1. BuLi, THF , -78°C 2. PhCHO, -78OC -+ rt

+

PhxH

/= 85%

MO, X.-S.; uuang. Y.-Z, Tetrahedron Lett., 1995, 36, 3589

&

OMe Dibal , 14% Ni(cod)z 20% R-BINAP , lh i-l

OMe

*

H

htens.

78% (97% ee) M; Chiu, P.; Ma, S.; Rovis, T. J. Am. Chem. SOC.,1995, 117, 532

‘OMe

Aldehyde – Amide

Section 335

283

Ph SnCb-NBu3 , MeCN reflux Yamaguchr. b&; Hayashi, A.; Hirama, M. J. Am. Chem. Sot., 1995, 117, 1151

S.-K,; Park, D.-C.;

Rho,

H.-S.; Yu, C.-M.; How

J.-H,Synth. Commun., 1995, 25,

203 OMe =c

PhCHO .

9 10%Ti(OiPr)d

20% chiral binaphthylamine

Bemsford.

.

C, Angew. Chem. Znt. Ed. Engl., 1995, 34, 1717

Also via:

Section 302 (Alkyne – Alcohol).

SECTION 333: ALDEHYDE

– ALDEHYDE

NO ADDITIONAL EXAMPLES

SECTION 334: ALDEHYDE

– AMIDE

S02Ph

SO2Ph Brown, S.; Clarkson, S.; Grigg. RJ Sridharan, V. J. Chem. Sot. Chem. Commun., 1995, 1135

SECTION 335: ALDEHYDE

– AMINE Cl DMF , POC13 8%

Balasundaram, B.; Venugopal, M.; Permumal.P.T, Tetrahedron Lett., 1993, 34,4249

284

Compendium of Organic Synthetic Methods, Vo19

SECTION 336: ALDEHYDE

– ESTER

NO ADDITIONAL

SECTION 337: ALDEHYDE

EXAMPLES

– ETHER, EPOXIDE, THIOETHER

ct

Wp-OMe)2KOD)2

10 eq. PPh3 , CO, H2

+

+ HC(OEt)3 ,2d (96 + HC(OEt)3 + PPTS ,12h (0 Femandez, E.; B. S, Tetrahedron Lett., 1994, 35, 2361 2% Pd(PPh3)4,5 atm CO, THF C5Hll

4) loo)

PhSH , 70°C , 16h

Et0 quant. quant.

CHCHO PhS

Ogawa. &; Takeba, M.; Kawakami, J.; Ryu, I.; Kambe, N.; &poa 1995,

82% (13:87 E.-Z) N, J. Am. Chem. Sot.,

117, 7564

SECTION 338: ALDEHYDE

– HALIDE, SULFONATE

NO ADDITIONAL

SECTION 339: ALDEHYDE

SECTION 340: ALDEHYDE

EXAMPLES

– NITRILE

NO ADDITIONAL

SECTION 341: ALDEHYDE

EXAMPLES

– KETONE

NO ADDITIONAL

EXAMPLES

– ALKENE

For the oxidation of allylic alcohols to alkene aldehydes, also see Section 48 (Aldehydes from Alcohols).

CHO

1. Cp$r(Cl)CH=CHOEt cat. AgClO4

2.H3O+ oMaeta, H.; Suzuki. K, Tetrahedron Lett., 1993, 34, 341

OEt

C5h *

L

Section 341

285

Aldehyde- Alkene

Section 341

Li 1.

OMe

-78OC+ 0°C

PhCHO 2.1N

*

CHO P

HCl , OmC

75%

Duhamel, I,,; Duha.mel,P.; Le Gallic, Y. Tetrahedron Lett., 1993, 34, 319

OTMS 0 I

OTMSCAN, MeCN , O°C

Paolobelli, AX; Latini, D.; Ruzziconi.

25%

CHO

Tetrahedron Lett., 1993, 34, 721

polymeric Fe catalyst

Saha,AK.; Hossain. M.M, Tetrahedron Lett., 1993, 34, 3833 Br

CHO 6

/

9 (3-W& 79%

cyclic B catalyst, -78°C ,8h

(99:l exxendo) ,92% ee Corev. E.J,; Loh, T.-P. Tetrahedron Lett., 1993, 34, 3979

PhCHO

CsF-DMSO , rt + loO°C

*

PWCHO

ZnClz, rt ,2h &; Salemkour, M. Tetrahedron Lett., 1993, 34, 5281

70%

2.

md.

7=-i

PhCHO ,5% TfSiMe3 CH2C12, rt ,15h

P

v MqSi CHO OSiMe3 Duhamel. L; Gralek, J.; Bouyanzer, A. Tetrahedron Lett., 1993, 3% 7745

80%

Com~n~um of Organic Synthetic Means, Vol9

286

N-t-Bu md.

WI,: 1187

PhCHO , 10% ZnBrz , THF

(Me3Si)zHC J a; Majidi, A. J, Org. Chem., 1993, 58, 2517 m

/CHO

Section 341

SnBq

, CgHlyBr, AIBN

20 atm. CO, PhH , 80°C, 8h

Yamazaki, H.; Ogawa, A.; Kambe, N.; ma.

1.

9 0

74% N, J, Am. Chem. Sot., 1993, 115,

, acetone

a2. PH3P=CHCH0, CH2C12

‘“~0, 84%

Adger, B.J.; Barrett, C.; Brennan, J.; McGuigan, P.; Wervey. Commun., 1993, 1220

M.A, J. Chem. Sot. Chem.

HO , SmI2,25OC

CHO (955 Van de Weghe, P.; collin,

[1,4:1,3])

72%

Tetrahedron Lett., 1994, 35, 2345

Bu 1. Bu$H , TiCI , CH2Cl2 2. F’OC13 , DMF , O-5OC

67%

*

~

CHO

Asokan. CV,; Mathews, A. Tetrahedron Lett., 1994, 35, 2585

75 Derien, S.; Dixneuf. P.I-I, J. Chem. Sot. Chem. Coals.,

25) 85%

: 1994, 2551

Ph-OH

287

Amide – Amide

Section 342

Pd(PPh3)4 , NH4PF6 , toluene – phmcHo 02 , heat

90% Gomez-Bengoa, E.; Noheda, P.; Echavarren, A.M. Tetrahedron Lett., 1994, 35,7097 Et0

SnBu,

1,

PhCHO

ph/n/CHO

BF3mOEt2, CH2C12, -78OC, lh 86% Cabezas, J.A.; Oehlschlaner. AC, Tetrahedron Lett., 1995, 36, 5127

.

Mn02, hexane, 15 mm

ph-N,OH

*

phmCHo 87%

Shinada, T.; Yowa.

L Tetrahedron Lett., 1995, 36, 6701 CHO Ru (indene)Cl(PPhg)z

88%

-i_i

Ph

Ph

Trost, B.M.; Livingston, R.C. J. Am. Chem. Sot., 1995, 117, 9586 CHO

2% [ Rh(CO)z(acac) ] +

C3H-W7

2.2% biaryloxyl phophite

Johnson, J.R.; Cuny, G.D.; mwald.

SLAngew.

A C3H7

w7

85% Chem. Int. Ed. Engl., 1995, 34, 1760

Also via P-Hydroxy aldehydes: Section 324 (Alcohols – Aldehyde).

SECTION 342: AMIDE – AMIDE NO ADDITIONAL

Also via Dicarboxylic Acids: Diamines

EXAMPLES

Section 312 (Carboxylic Acid – Carboxylic Acid) Section 350 (Amines – Amines)

288

Compendium of Organic Synthetic Methods, Vol9

Section 343

SECTION 343: AMIDE – AMINE Me C=N

AcCl , Ac20 , HCl 63%

100-130°C) 4h

NHAc Me Vijn. R.J,; Arts, H.J.; M aas, P.J.; Castelijns, A.M. J. Org. Chem., 1993, 58, 887 l.TMSCI,NaI,12 TMEDA , MeCN 2. NH3, loO°C 3. racemization-resolu tion

o-II& K.L; Keller, J.L.; Purick, R.M Hartner Jr., F.W.; Choi, W.-B.; Askin, D.; Volantei R.P. Tetrahedron Mt., 1994, 35, 32i9 l

TsHN

Pd(OAc)z , EtzNH latmCO,THF

P

,-Ts

CH2Ch

. Andersson. PeGI; Aranyos, A. Tetrahedron Lxtt., 1994, 35,444;

/ I q

14) 72%

Me -7OOC + -2OOC

N

I N

t Ph

OZnCl OMe

Me0

58%

Me van Maanen, H.L.; Kleijn, H.; Jastrezebski, T.B.H.; van Koten. G, Reel. Trav. Chim. Pays-Bas, 1994, 113, 567

Section 344

Amide – Ester

T

289

S

N

BnNH2,10%

NHTs

Yb(OT&

CH2C12, rt, 1Oh

NHBn

ANHBn

‘arts

A

(>99 : 1) Meguro, M.; Asao, N.; Yamamoto, Y. Tetrahedron L&t., 1994, 35, 7395

CL N

0

t-BUN& , NEt3

)

0%

N

75%

0

78%

CH2C12, reflux , Id I Cl NHt-Bu Chen, P.; Suh, D.-J.; Smith. M.B, J. Chem. Sm., Perkin Trans. I., 1995, 1317 L

SECTION 344: AMIDE – ESTER t-BuBr , KgO3, DMAC BTEAC ,55OC * Boc

92%

BocH DMAC = dimethyl acetamide BTEAC = BuEt3NCl Chevallet, P.; Garroust, P.; Malawska, B.; Martinez. J. Tetrahedron L&t., 1993, 34, 7409

Mn(OAc)3 , CH$O2Me)2

Chuang. C-P,; Wang, S.-F. Tetrahedron Lett., 1994, 35, 1283

a;

Lee, S.J. Tetrahedron Lett., 1994, 35, 1875

290

Section 345

Compendiumof Organic Synthetic Methods, VoI9

1.15% ZnCl2 CH2C12 2. CAN, M&N, CO

Ph

Ph Chen, T.; Jiang, S.; mos. E, Tetrahedron Lett., 1994, 35, 8325

Y

Cl

CO2Me Bu3SnH , AIBN , PhH *‘h0

N’Bn

Ph “i( 0

N I Bn

2:

C&Me

Ph 0

52% Goodall, IL; Parsons.A.F, J. Chem. Sot., Perkin Trans. I., 1994, 3257 0

1. Sn(OTf)z CHz,Clz

0

C02Me

~

N– Et

c

2.

N

**

c-l

I

OEt

COzMe

C02Et

‘;J

CO,Et

78% Nagasaki; Nishida, S.; Sugihara,S.; Kawahara,T.; Adachi, K.; Hamaguchi,F. ~etero~c~s, 1994, 39, 171 Section315 (Carboxylic Acid – Amide) Section316 (C~~xy~ic Acid – line) Section 351 (Amine – Ester)

RelatedMethods:

SECTION

345: AMIDE

– ETHER,

EPOXIDE,

THIOETHER OH

CO/H2 (1600 psi) ,loO*C HC(OEt)3,24h H~(CO)(PPh)3 OSiMe3

42% OEt

0

(2: 1 syn:anti)

Eguchi, M.; Zeng, Q.; Korda, A.; Qiioma. I, Tetrahedron Lett., 1993, 34, 915

291

Amide – Ether

Section 345

1.

P-O H

Ph Ph

J3H3,TNF

w

2. H+ , EtOH Bn Romagnoli, R.; Roos, E.C.; Hiemstra. H,; Mollenaar, M.H.; Sneckamp,W.N.; Kaptein, B.; Schafer, H.E. Tetrahedron Lett., 1994, 35, 1087

H

Ar

Ar = 4-nitrophenyl; Ar’ = 4-t-butylphenyl

95% (66% ee) Hayashi, M.; Ono, K.; Hoshimi, H.; Qgni. N, J. Chem. Sot. Chem, Commun., 1994, 2699

cyclohexanone, H$X&

CN AcOH , Ac20, 10°C , Ih a&. J.-F,; Jung, L.; Hug, R. Heterocycles, 1994, 38, 297

cat. ZnC12, CH2C12,50°C16d ~y~e~ic

Pummerer rearrangement

; Shibata,N.; Kawano, N.; Tohjo, T.; Fujimori, C.; Matsumoto, K. Tetrahedron Lett., 1995, 36, 115

Section 346

Compendiumof Organic Synthetic Methods, Vo19

292

[email protected]

Amlres, C.J.; Spetseris,N.; Norton

SECTION 346: AMIDE – HALIDE, SULFONATE

Cl * l-L?Cl

Cl

CuCl , cat. bipy

98%

0

N

I Bn

Nagashima,H.; Ozaki, N.; Ishii, M.; Seki, K.; Washiyama,M.; Itoh, K. J. Org. Chem., 1993, 58,464

Et3N*3 HF , MeCN

77%

t e”

Narizulca, S.; Fuchierami. T, J. Org. Chem., 1993, 58, 4200

IP

Ph#e(OH)OAc , I2 hv ,6Sh ?

0

I

I

76% Dorta, R.L.; Francisco, C.G.; Suarez. IE,~etr~he~~~~ Lett., 1994, 35, 1083

a

NPh2

w ~

.

h/L; m

1. b-AnP(S)S]z, PhMe , lOO*C 2. Bum2F3, NIS , CH2C12 o”c -+ l-t T, ~etr~he~~u~ Lett., 1994, 35, 3983

F w w

x

F

NPh2 98×64%

Section 347

Amide – Ketone

293

C3H7

0 b Nt

0

-7VC, 6h BC120Me

ind Jt-

1) 80% o. G,; Di Martino, E.; Gentilucci, L.; Tomasini. C,; Tomioni, L. Tetrahedron Asymmetry, 1995, 6, 1957 (>99

l

SECTION 347: AMIDE – KETONE

0

2DMP,4Py,lh CH2Clz, rt

N

Dess-Martin

ti

)

0 N

0

periodinane

Ph

75%

Ph

,hyr DMP = 1,1,l-triacetoxy-l,l’-dihydro-l,2-benzodoxol-3(1H)-one Batchelor, M.J.; Gillespie, R.J.; Golw. J.M.C,; Hedgecock,C.J.R.

Tetrahedron Lett., 1993, 34, 167

30% H202, Pd(OAc);! CH2C12,rt ,2h –

73% *

Naota, T.; Sasao,S.; Tanaka,K.; Yamamoto,H.; Murahashl.. 4843

0

0

ii Tetrahedron Lett., 1993, 34,

OEt

w

c

0 TFA , 20°C, Id N

NT -* 0 Br 0 J.-P*;Jacquesy,J.-C.; R~nbaud, D. Tetrahedrons 1993, 49, 2239

47%

Section 347

Compendium of Organic Synthetic Methods, Vol9

294

Bu$nH, AIBN, PhH (syringe pump addition) a 91%

Beckwith. A.L,J,; Joseph, S.P.; Mayadunne, R.T.A. J. Org. Chem., 1993, 58, 4198

1. 3 Mn(OAc)3 2. H30+

+

h /

N

cossy. J,; Bouzide, A.; Leblanc, C. Synleft, 1993, 202 OTMS Me$iOTf

NMeC02Mk

, NEt3

NMeC02Me

O°C , lh Rossi, L.; J?ecumo. OMe

A, Tetrahedron Lett., 1994, 35, 5285

)I

Hewawasm

3.12N HCl-DME , reflux /

Me 0

1. BuLi, THF, O°C 2. (C02Et)2

I b

85%

I fi

0 /

NHCOzt-Bu P,; Meanwell, N.A. Tetrahedron Lett., 1994, 35, 7303

PhCH=NC02Et,

BF3eOEt2

CH2C12, rt ,2d ten Hoeve, W.; Wynberg, H. Synth. Commun., 1994, 24, 899

N H

80×88%

section 347

Amide – Ketone

295

Me I

1. Me~OH

Ph

0 N-Me

2.

60% via heteroCope 3, Hz0 Lantos, I.; Zhang, W.-Y. Te~$~~e~r~~ L&t., 1994, 35, 5977 0

OMe Si(iPr) 3

1. RCOCl 2. MeMgX 3. oxalic acid 4. TFA , CHC13, heat + ,yyi+* ,* i) N

I

I 78~86% I CO2R

R = (-)m8-phenylmen~yl Comins. D.L,; LaMunyon, D.H. Tetrahedron Lett., 1994, 35, 7343

1. t-BuLi , TMEDA , -78OC NiPr2

t 2.

Brenstrum, T.J.; Brimble. M.A,; Stevenson,R.J. Tetrahedron, 1994, 50, 4897 0

NHAc

I /I phi 0

CoCl2, MeCN, AcCl

Bhatia, B.; Reddy, M.M.; Iqbal. J, J. Chem. Sot. Chem. Commun., 1994, 713 b

NfIMe

4 eq. DMAP , toluene , reflux

N

/

Me

w

c0ssv.z.; Belotti, D.; Bouzide, A.; Thelland, A. Bull. Sot. Chim. Fr., 1994, 131, 723

NO2

Section 349

Compendium of Organic Synthetic Methods, Vol9

2%

0

* 0”

l.e-,AcOH,heat 2. MeOH, NazCO3

0

75×95% N N I I C02Me C02Me Matsumura. Y.; Takeshima, Y.-i.; Okita, H. BUZZ.Chem. Sot. Jpn., 1994, 67, 304

iPrCH0, AcCl ,02, CoC12 = Reddy, M.M.;

MeCN Bhatia, B.; -1.

76%

J, Tetrahedron Lett., 1995, 36,4877

0 cat. [Rh2(OAc)4] B-‘&/2

=: = z

*

59%

Ge Podlech, J.; Seebach. D, Helv. Chim. Acta, 1995, 78, 1238

SECTION 348: AMIDE – NITRILE 0

0 CN

IIZN JL

Ph

CN

DMSO, O2 Ph

88% Jain, R.; Roschangar, F.; Ciufolini. M.A, Tetrahedron Lett., 1995, 36, 3307

SECTION 349: AMIDE – ALKENE

.. (6 Khiar. NJ Femandez, I.; Alcudia, F. Tetrahedron L&t., 1993, 34, 111

4

78%

297

Amide – Alkene

Section 349

1. LDA , THF , -78OC ApcPh

92%

PhR 2. PhCHO , THF Ph I /q II I ph reflux Me Me 0 ; Deniau, E.; Grandclaudon,P. ~~tr~h~~ron Lett., 1993, 34, 1479

0 /

0

0

lm%z

, MS481, CH2C12

0

*

20% chiral Yb triflate , O°C

~~ .

I(lobavashl.;

(89: 1 en.do:exo; 95%ee) Hachiya, I.; Ishitani, H.; Araki, M. tetrahedron Lett., 1993, 34, 4535

4% Pdz(dba)3eCHC13 9.6% RS-BPPFOH silver~xch~ged zeofite c ~~ ~

D~:DMSO

0 (1

0

Tetrahedron ktt.,

Nukui, S.; Sodeoka,M.;

Bf R -dFoEt

+

, WC, 5d

*.

1.4) 94% (86%ee)

1993, 34,4965

, PPh3 /n-IF

Ph

f14$.?

R

Ph

2% Pdz(dba)3~HCl3 2 eq. iPr2NEt

OEt

g

0

N

73%

Bn Torii. &; Okumo~, H.; Sacked M.; Hai, A.K.M.A.; Tanaka, H. tetrahedron Lett., 1993, 34, 6553

0 I

) -20”C, 36h

Ph

w

b&imine*cu(OTE)2 (>97:3 en.do:exo) 72% Evans. D,A,; Lectka, T.; Miller, S.J. Tetrahedron Mt., 1993, 34, 7027

298

Section 349

Compendium of Organic Synthetic Methods, Vol9

1.. 0.2 eq.fe(acac)s 3 eq. EtjAI/L

0

o+

2. ethylene glycol cat. p-TsOH cc BzO

ws.

m;

Weidner, J.J.; Takacs, B.E. Tetrahedron Mt., 1993, 34, 6219

0.02 PdC12,2 eq. CuCL2 3 eq. ClCH,CQ-Na+ NHTs 9(

C02Me

CO. MeOH

N

53%

Ts

Y

0

0 Kimura, M.; Saeki, N.; Uchida, S.; Harayama, H.; Tanaka, S.; Fugami, K.; Iama~~ Y, Tetrahedron Lett., 1993, 34, 7611 1. Et02C-N=N-COzEt , SnC4 CH2C12, -60°C, 5 min

2 N-J-N

*

*mC02Et

2. Li , NH3 , -33°C 3.10 N HCl Brimble, M.A.; -cock.

CL

87 x 86% (1l:l

E:Z)

J. Org. Chem., 1993, 58, 5261

Br Pd(OAc)z , P(o-ToI) , DMF Na$ZOs, BUflCl ,65”C, 40h sealed tube (in vacua) 4iEs+

&

1) (4 Harris Jr., G.D.; Herr, R.J.; Weinreb. S.M, J. Org. Chem., 1993, 58; 5452 l

78%

Amide – Alkene

Section 349

299

Pd(PPh3)4,PhMe ,lOO°C Trost. B.M; Marrs, C.M. J. Am. Chem. Sot., 1993, 115, 6636 COzBn Ph$‘=CHCO2Et *

80%

toluene , reflux ,4h

Et0 ~ Ba: 0 BOC Baldwin. JE,; Edwards, A.J.; Farthing, C.N.; Russell, A.T. Sy~lett, 1993, 49 CO2Me

1. NaH , THF , BuLi CO2Me Ts

>96% (>20:1 E=z)

3. toluene , Amberlyst 15 , reflux &p

B, Sy~~ett, 1993, 764 Ph PhCH2m2Et

Ph

1.2 eq. LDA 2. Ph~H=NPh

*

PhHN 7

58% 0 this reaction forms a p-lactamwith 1 eq. of LDA Manhas. M.S; Chaudhary, A.G.; Raju, VS.; Robbi, E.W.; Bose, AK. HeterocycZes, 1993, 35, 635

1. xylenes , reflux 2. PPTS NaH , DMF THPO’ De la Torre, J.A.; Femandez,M.; mJr.. Tetrahedron Lett., 1994, 35, 15

60% 68~75% D,; Smith, D.B.; Talamas,F.X.; Trejo, A.

OMe Zn,THF,rt,lh NHCaMe Kise. N,; Yamazaki, H,; Mabuchi, T.; Shono, T. Tetra~e~r~~ Lett., 1994, 35, 1561

300

Section 349

Compendiumof Organic Synthetic Methods, Vol9

79% W,; Fiirstner, A. Helv. Chim. Actu, 1993, 76, 2329

Qpolzer.

1. piperidine , [email protected] –YSPh

THF’rt 2. [email protected] NiCl,(dppe)

6

* csH1& , THF , 0°C + rt 57×60%

a

B&u&-i, F.; Fiandanese.V,; Naso, F.; Punzi, A. Tetrahedron Lett., 1994, 3.5, 2067

6 i/

PhMe2CCH=Mo-N[2,6-(iPr)2C6H13] [ocMe(CF3)212

N-0

I

[email protected]

PhH,rt

0

80-90%

/

n. S.F,; Liao, Y.; Chen, H.-J.; Patzel, M.; Ramser,M.N. Tetrahedron Lett., 1994, 35,

&‘Ph3

SO2Ph

Burley, I.; Hewson. A.T, Tetrahedron Lett., 1994, 35, 7099

COzt-Bu

C02t-B u 52% (9O:lO E:Z)

Wei, Z.Y.; m.

EL Synlett, 1994, 345

Section 349

Amide – Alkene

301

0 ==cIl N

, MS 4A, CHg12

alto

N CA

/ N

20% Yb-BINOL complex 7

0

c-J== 0

Me

0

.t

(89

11) 77%

95% ee Ishitani, H.; Araki, M.; Hachiya, I. Tetrahedron Lett., 1994, 35, 6325

.

WS.;

0

C02Et NH2

1. C02Et

.

Me”“’ rl Ph

H

, BF3GEt2, PhH , reflux

2. [email protected],

0

TI-IF , reflux

+Jz+If2

N

Me”““’ri Ph

H 76% (97:3)

Barta, N.S.; Brode, A.; Stille. J.R,J. Am. Chem. Sot., 1994, 116, 6201 Ar NH2

H2C0, [Rh(OAc)d2, PPh3, PhH -Iso 0

N I 40% H Campi, E.M.; Chong, J.M.; Jackson. W.R,; Van Der Schoot, M. Tetrahedron, 2994, 50, 2533 Ar

aI/

NHTs

I

I

Ts CsI-I17–CH=C=CH2 Ag3P04, 5% Pd(OAc)z

/ w-h7

his-oxazoline catalyst 90°C, Id, DMF 94% (82% ee)

Larock. RC,; Zenner, J.M. .I. Org. Chem., 1995, 60, 482

302

Compendium of Organic Synthetic Methods, Vol9

Section 349

Ph-N=C=O , AlC13 ,4O”C Men&Me

ti

NHPh

Me 9

3

CH2C12, 12h 0 Niestroi. M,; Neumann, W.P.; Thies, 0. Chem. Ber., 1994, 127, 1131

50% (4.9:1 E:Z)

BQNF ,66OC

Bn Jacobi. P.A,; Brielmann, H.L.; Hauck, S.I. Tetrahedron L&t., 1995, 36, 1193 Bu 5% C12Pd(PPh&, MeOH, 65OC *

CO (1 atm) ,4 NEt3

AcAB’

ci,

0

N I AC

78%

Coperet, C.; Sugihara, T.; Nenishi. E, Tetrahedron L&t., 1995, 36, 1771 phwTePh

TsNNaCl , EtOH ,20h 25OC

Nishibayashi, Y .; Srivastava, SK.; Ohe, K.; Ueu

c),

-‘“‘f‘

+PhyNHTs

OH 9% 84% Tetrahedron Lett., 1995, 36, 6725

1. LiHMDS , THF , HMPA , -78OC 2. PhNTf2, -78OC + 25OC

cl

t

N o 3. PhguLi , THF-HMPA I -78OC + 25OC Bz Tsushima, K.; Hirade, T.; Hasegawa, H.; Murai. A, Chem. Lett., 1995, H Me+,,,,

I 9(

Me 0.1 AgNCO , 0.1 NEt3 , PhH 50°C, 5h NHTs

N I Bz 801

94×69% Ph

-w/r”“’ N-Ts

-lf

0 0 Kimura, M.; Tanaka, S.; Tamaru, Y kBull. Chem. Sot. Jpn., 1995, 68, 1689

98%

Section 350

Amine – Amine

303

Also via Alkenyl Acids: Section 322 (Carboxylic Acid -Alkene)

SECTION 350: AMINE – AMINE In , aq. EtOH , 16h ) NH&l

N /Ph PhJ

Ph Ph NHPh quant.

NHPh Kalvanam. N,; Rao, G.V. Tetrahedron Lett., 1993, 34, 1647

Plaquevent. J.-C,; Chichaoui, I. Tetrahedron Lett., 1993, 34, 5287 NH

PhCN H

quant.

* G+ Ph Rousselet, G.; Candevielle, P,; Maumy, M. Tetrahedron Lett., 1993, 34, 6395

NHEt2 ,0.8 GPa , CH2C12 ,2d MeOH, 50°C

H

68% H Matsumoto. K,; Uchida, T.; Hashimoto, S.; Yonezawa, Y.; Iida, H.; Kakehi, A.; Otani, S. Heterocycles, 1993, 36, 2215

/

Br

1. t-BuLi , -78OC , THF 2.ZnC12 3. PdC12(PPh3h , Dibal THF , reflux * w

SiMeg-Bu

Br

/

Ior)

4. TsOH , EtOH Amat, M.; Hadida, S.; Bosch., J. Tetrahedron Lett., 1994, 35, 793

/

93%

N SiMe$-Bu

Compendiumof Organic Synthetic Methods, Vo19

304

AI,KOH,MeOH,rt,lOmin 2 ph-

Section 351

Ph

Ph

t

NPh

PhHN Baruah, B.; ~ajapa~, ID.; mu.

NHPh

90% (70:30 dlmeso) J& Tetrahedron Lett., 1995, 36,6747

(95 N&

Nh

. OH Ar = 4-OMe phenyl Shimizu, M.; Kami, M.; EU,jisawa.T, Tetrahedron Lett., 1995, 36, 8607

5) 71%

l

SECTION 351: AMINE – ESTER

C

1.

COzEt ~echoech~;

COzEt

I”

2, SmI2, THF ,25OC 70%

Fem~~dez-Acebes, A. Tetr~~dro~ Lett., f993,34,549 Ph

N I

1. ImzCO , BF3*OEt2

PhHN

84%

c( 7

TMS

AgF , EtOAc >

s

MeCN , rt 15 min TM:

(17 m.

COzMe

‘t

THF , heat Y 2. NaOMe , MeOII/THF 94% ph S,; D&u, M.D.; CarkSn,R.P. Tetrahedron Lett., 1993, 34, 725 PhA

m.

N-H

(7:3 de) G; Lakshmaiah,G. Tetrahedron Lett., 1993,34,4861

..

SC ss, C02Et 3)

98%

Section 351

305

Amine – Ester

I P

1.

, BEt3, DMSO C02Et

54%

Fe2(SO)3~H20, hexane

. Me ch;L,E;,Muraglia, E. Te~rah~dru~ Let?., 1993, 34, 5015 Ph Ph

OMe

78:22 (anti:syn) * dried under microwave condi~ons Texier-Boullet. F,; Latouche, R.; Hamelin, J. Tetrahedron Let?., 1993, 34, 2123

m. .

P,; Pastor,A.; Vilaplana, M.J. Tetrahedron Lett., 1993, 34, 3773

1. Na+ NHS02Tol,60°C THF/DMSO, 19h ) M~~Npha~ -0Ac 2.03, NaOH/MeOH -78OC, 3h Jumnah, R.; Williams. J.M.J, Tetrahedron L&t., 1993, 34, 6619

90%) Et2N+ +‘“‘, )

PhOqwt2

2. PhOH , NaOH , THF C8h7

C8h7

61% 30% Richardson, P.F.; Nelson, L.T.J.; Shamless.K.B. Tetrahedron Lett., 1995, 36, 9241

17

0

hv , PhSH ,2h

fl

N

..

(82

6:12) 66%

trans:cis Naito. T,; Honda,Y.; Miyata, 0.; Ninomiya, I. J. Chem. Sot., Perkin Trans. l., 1995, 19

SECTION 353: AMINE – HALIDE, SULFONATE Br2, CH2C12 0.5 MeOH * 0.01 Et3NHCl

Brr-(=)-NMe2 near quant.

Gervat, S.; Lbnel, E.; Barraud,J-Y.; Ratovelomanana. V, Tetrahedron Lett., 1993, 34, 2115 “Ni;?B” , H20,15OC ,30 min 72% “Ni2B” = Ni(OAc)2.4 HzO/NaBHd Seltzman. H.H,; Berrang, B.D. Tetrahedron Lett., 1993, 34, 3083

312

Compendium of Organic Synthetic Methods, Vol9

Section 354

CF3SiMe3 , THF Etw, 15h,rt

Felix, C.P.; Khatimi, N.; Laurent.

Tetrahedron Lett., 1994, 35, 3303

mco2Et 0

iPrOH,HCl(+rt+ CN

I H

Foley. L.H, Tetrahedron Lett., 1994, 35, 5989

96%

SECTION 354: AMINE – KETONE

C Rechsteiner, B.; Texier-Boullet,

+ ON I

t

0

microwave (300W) 3 min

UPh

0I /

, SiO2

N-H

F.; j-bnelin.

O- Li+

0 TfO-

-78OC

+

89%

J, Tetrahedron Lett., 1993, 34, 5071

/rHF

*

*35%

23OC

F . Kiselyov, A.S.; &&QWS~ I,, J. Org. Chem., 1993, 58, 4476

hv ,9,10-dicyanoanthracene

Zhang, X.; Jung, Y.S.; -0. 1993, 34, 5239

P.S.: Fox. MA;

78% Martin, P.S.; Merkert, J. Tetrahedron Lett.,

Section 354

Amine – Ketone

313

hv*

c

Winkler. JD,; Siegel, M.G. Tetrahedron Lett., 1993, 34, 7697

2

Me

hv ,9,10dicyanoanthracene MeOH/MeCN

,,o*,Me

M fd ,\-

Bn

N

Bn 23% at 73% conversion

TM .

Khim, SK.; Marianr,. PLS, Tetrahedron Lett., 1994, 35, 999

0

0

0

O

PhNH;! , PhH , reflux

-*

*

0

0

0

N I Ph

90% Adembri. G,; Celli, A.M.; Lampariello, L.R.; Scotton, M.; Sega, A. Tetrahedron L&t., 1994, 35,4023

CT NH2

I

N

/

1. PhCHO 2. TMSOTf , MeCN acetophenone

*

&q- THF , -78OC

Wegman, S.; Wiirthwein. E.U. Tetrahedron Lett., 1993, 34, 30;

0 N

PhCHO

M

+

cat. PdC12(PPh3)2 Me

K2C03

I (E+Z)

Ph in Toluene 10% 85% in DMF 72% 2% Filionini. L,; Gusmeroli, M.; Riva, R. Tetrahedron Lett., 1993, 34, 1643 0

OBu

1. LDA , -78°C THF + xylene

2. xylene , reflux ,4h b,tiHBu

moda.

+

&HBu

(99.5 : 0.5) 92% T,; Tats&i, S.; Shiraishi, Y.; Akasaka, M.; It& S. Tetrahedron L&t., 1993, 34, 3297 OMe OMe

1. BF3aEt2, 2. crc12

THF

3. ally1 bromide , rt P

4. 10% aq. Na2C03

Giammaruco, M.; Taddei. M,; Ulivi, P. Tetrahedron Lett., 1993, 34, 3635

65%

Section 356

Amine – AIkene

N3

317

[email protected]‘t-

1. PPh3

+

2

%@Et

l

C02Et

Et02

C02Et

am-

EtO$

Y

92%

0

Palacios.F,; Perezde Heredia, I.; RubiaIes,G. Tetrahedron Lett., 1993, 34,4377

. -K.;

.

Kaneko, M.; Yajima, T. Tetrahedron L&t., 1993, 34, 4841 h

Bu$nH , AIBN ,O.O5M (syringe pump) ,2h

NHPh

h +

*

pi

/

PA

Phvv

SePh

45%

23% Refvik, M.D. Tetrahedron Lett., 1993, 34,490l

Schvvan.;

Me$ (CH20)n, p-tsOHaH20 MeCN ,6Q*C

67-69% (64-67%ee) 4’J4Hb,,*,

Bn

$

Bn

H Castro, P.; Ovem

J&;

Zhang, X.; &briano, P.S, Tetrahedron Lett., 1993, 34, 5243 t-BuNH2, MS 3A, 2h CH2C12,22*C

*

P

Merrr,,, t-B

94%

Sigman, M.S.; Eaton. B.E, Tetrahedron Lett., 1993, 34, 5367

t-Bu H

318

Compendium of Organic Synthetic Methods, Vol9

Section 356

Pb

l.LDA.THF

78% de1 Pozo Losada, C.; Olano, B. Tetrahedron Lett., 1993,34, 5497

Barluenu;

Bi/BuflBr

, MeCN

PON-Pb -Br

Bbuyan, P.J.; Prajapati, D.; Sandhu, JS, Tetrahedron Lett., 1993, 34, 7975

N Cb

, toluene , bv I

2

CH20Et

2.23OC, 12b 3. TBAF

N

N c

d N CH20Et

91%

Knapp. S,; Albaneze, J.; Schwar, H.J,J. Org. Chem., 1993, 58, 997

(66

..

34)

I Bn

Pb

Bebolz, L.G.; Stille, J,R, J. Org. Chem., 1993, 58, 5095 Phi , Pd(PPh& K2CO3 DMF , 70°C NHBn Davies, I.W.; Scopes, D.I.C.; Gallagher, T. Synlett, 1993, 85

99%

Section 356

Amine – Alkene

319

SnBu3 Bn

.I

;;IJJTY

yHBn+

p-Me

. (17 Coldham. I, J. Chem. Sot., Perkin Trans. I., 1993, 1275

83) 65%

l

Leurs, S.; Vanderbulcke-Coyette,B.; Viehe, H.G. Bull. Sot. Chim. Be&., 1993, 102, 645

V9:nzBr3

NHPh

DMF

*

PhL

Jin, S.-J.; Araki, S.; Butsunan. Y. Bull. Chem. Sot. Jpn., 1993, 66, 1528

N

/

SEt

Bn A

w H

AlC13, CH&

, rt

voms NHBn

OTBS

84%

SEt

r 77% Tohyama, Y.; Tanino, K.; Kuwajima. I, J. Org. Chem., 1994, 59, 518 I

4 w

NHTs

Br ’

5% Pd(OAc);!

N 10%P(o-Tol)3 , Na2CQ I -Ko Ts 88% 2 [email protected] ,9O”C, Id Larock. RC,; Yang, H.; Weinreb. S.M,; Herr, R.J. J. Org. Chem., 1994, 59, 4172

320

Com~n~um

of Organic Synthetic Methods, Vo19

Bernard-Henriet, C.; Grimaldi, J.R.; Hatem.

Section 356

NHNMe2 89% Tetrahedron Mt., 1994, 35, 3699

N I

..

(2.7 pearsOn. W&;

Me 1) 65%

1

Jacobs, V.A. Tetrahedron Lett., 1994, 35, 7001 PhNHOl-l , FeC12/FeC13 72% *

Srivastava, R.S.; Nicholas,.M.

w

NHPh

tetrahedron Lett., 1994, 35, 8739

dco2t-Bu

L

C7Hl

LDA Ahman, J.; &&&j.

P,J, Am. Chem. Sot., 1994, 116, 9781

Ph-NW

1. Ni(cod);! , MeCN Br

45% 2.16 NaBH4,6 MeOH

Sol& D.; Cancho, Y.; Llebaria, A.; Moret6, J.M.; Del&ado. A, J. Am. Chem. Sot., 1994, 116, 12133

Amine – Alkene

Section 356

321

1% (PCy3)g12Ru=CHCH=CPh2 wPhH , eflux ,6h a &I 86%

‘OAc Kinoshita, A.; Mori. Synlett, 1994, 1020

– OAc –

-C-JO Fisher. GB,; Lee, L.; Klettke, F.W. Synth. Commun., 1994, 24, 1541 Ph Zn(Cu) , MeOH, H20, rt

/Ne . m.

Br

ultrasound

&, Jolie, R.; De Smaele,D. J. Chem. SE Chem. Cajun.,

1994,

53% 1221

Ph C02t-Bu

fN

/

LDA , TI-F , -78OC -n-

T

N I H

C02t-Bu

63% Coldham. I.; Collis, A.J.; MouId, R.J.; Rathmell, R.E. Tetrahedron Lett., 1995, 36, 3557

1

Et2N HNEt2, 20% Et3NHI, THF 10%Pd(dba)z,2 PPh3 65OC,

c7-h

b

18h

+

C7Ht

i J 70% (96:4 E.-z)

Besson,L.; Go&, J.; Gazes.

Tetrahedron Lett., 1995, 36, 3857

322

Compendiumof Organic Synthetic Methods, Vol9

Section 356

[email protected] Tf

4

NaCH(C02Me)2,5% Pd(PPh& LiCl , DMSO , 60°C

C02Me *

N Bn’

Vieart, N.: Gazes,B.; m C3H7

N

jBn

A v

53%

Bn’ Tetra~dron

Lett., 1995, 36, 50 15

ether, -5OOC-+ -1OOC,4h

Ph

*

F== C3H7

Ph

Ph

Proi/Ti

OiPr

Gao, Y.; Harada,K.; Usato, F. Tetrahedron Lett., 1995, 36, 5913 Ph Bu+i’–@ *

phi

15% Yb(OTf), , CH$12, rt N HN Ph Ph Bellucci, C.; Cozzi, P.G&;Umani-Ronchi, A, Tetrahedron Lett., 1995, 36, 7289 1. ~~~~~~ ph-NPh

NHPh

, Me$iCl

2. [email protected] 96%

Wang, D.-K.; Dai. L.-X.: Hou. X.-L, Tetrahedron L&t., 1995, 36, 8649 Ph2P

Ph2P

b

I

Ph w–h3

w-h3

(8

cc;&3 l .

1) 80%

(5:1 cis: tranws)

Didiuk, M.T.; Morken, J.P.; fioveysla. A& J. Am. Chem. Sot., 1995, I1 7, 7273

56%

Ester- Ester

Section 357

323

13F3*OEt2, 210°C ,2h w

Br Ph~

5 eq m~~huline , lOO*C 10 eq. H20, 2d

SECTION 357: ESTER – ESTER

~~~~H f AIBN , TuI reflux ,2h

*

0 Ph ; Kee, I.S. Te?~~~e~~~~Lett., 1993, 34,4213

2. Hfl 3. p-TsOH , toluene

Shimada, S.; Tohno, I.; Hashimoto, Y.;

*. 8) 85~ (92 Chem. Lett., 1993, 1117

324

Section 357

Compendium of Organic Synthetic Methods, Vol9

r

l/50 CoC12 ,42h *

r

OH

OCHO

DME , 02, 80°C

Li, P.; Alter.

H, Can. J. Chem., 1993, 0 C02Me

K

acetone, SmI2 , THF 4% Fe(dbm)3 , reflux

C02Me 74%

CO2Me

-b Imamoto. T,; Hatajima, T.; Yoshizawa, T. Tetrahedron L&t., 1994, 3.5, 7805 Mf30

OTMS

I Pd(PPh3)4, TlOAc OMe , HF reflux , Id 89% T,; Kondo, Y.; Masumoto, K.; Yamanaka, H. J. Chem. Sot., Perkin Trans. l.,

aoto. 1994,235

0

PhCHO , Cp2Sn(thf)2 0-

To1 , O°C + 25OC

A(&()‘ph

Takano, M.; Kikuchi, S.; Morita, K.; Nishiyama, Y .; m.

77% Y. J. Org. Chem., 1995, 60, 4974

NaB0~4 [email protected] , Ac20, PhH Ph Nag03,55OC,

14h 67%

Bhat, S.; Ramesha, A.R.; Chandrasekaran. S, Synlett, 1995, 329 Also via Dicarboxylic Acids: Hydroxy-esters Diols

Section 312 (Carboxylic Acids – Carboxylic Acids) Section 327 (Alcohol – Ester) Section 323 (Alcohol – Alcohol)

325

Ester- Ether

section 358

SECTION 358: ESTER – ETHER, EPOXIDE, THIOETHER Bu$W-I , AIBN sPhH reflux ,6h, syringe asp t

Lee.;

Br Tae, J.S.; Lee, C.; Park, CM, T~tra~dr~n Lett., 1993, 34,4831 Me3

A

P

OH

@Me

1. CsF , M&N 2,

Meo2 k

92%

C02Me

Hojo, M.; Ohkuma, M.; Ishibashi, N.;

Tetrahedron Lett., 1993, 34, 5943 OTMS

0

(Tf~)2Sn(bis~~ine) w CH2C12,9h , -78OC

Ph

EtS I

PhCHO

86~ (93:7 ~~n:a~ti)

Kobayashi, S.; IJchiro, H.; Shiina, I.; Mukaiyama, T. Tetrahedron, 1993, 49, 1761 OzEt

1.3Bu$nH 0.25 AIBN C.X&Et 0.03M PhH reflux ,8h

54) 91% (46 ; Tae, J.S.; Chong, Y.H.; Park, Y.C.; Yun, M.; Kim, S. T~tra~~dr~n Let& 1994, 35, l

129

CCHO

ems ===c,40% sno SEt

*

20% Sn(OTf);! chiral diarnine slow addi~ou (3h) ; Kawasuji, T.; Mori, N. Chem. Let& 1994,217

SEt 61% (62% ee)

326

Section 359

Compendium of Organic Synthetic Methods, Vol9

COZMe Rhz(OA& , MeOH

49% Tet~a~d~~~ Lett., 1994, 35,

Cox, C.G.; Haigh, D.; Hind~~y, R.M.; Miller, D.J.; 3139

0 CP “_/“e

1. PhCHO , ZnC12 , CH2C12 , rt 2. CAN, MeOH, -78OC, CO

= Me0 Ph

oc T~trahed~~~ Lett., 1994, 35, 7889

Jiang, S.;

~cl2-AgPF6, MeO$

COzMe

CH$&

CO,n/le

=

MeOH

*

MeO$Z

f==c

C02Me

quant. Kataoka, Y.; Ma~umot~, 0.; Ohashi, M.; Yamagata, T.; Tani. K, Chem Lett., 1994, 1283

SECTION 359: ESTER – HALIDE, SULFONATE [CF2Br$Z#n, DMF ,2h, rt] HMPA , CuBr , 60°C, 40 min *

98% 0

0 Mawson, S.D.; Weavers. R,T, Tetrahedron Let& 1993, 34, 3139

HoqoH

3HBb~~,lhh_

Bc

= S

= r:

=: =

= =

$H

&H

XAc

XAC

2.2 MeCOBr , dioxane ) 16h

/

80% El Anzi, A.; Benazza, M.; Frechou, C,; Demaillv, C, Tetrahedron Lett., 1993, 34, 3741

Br

Ekter- Halide

Section 359

327

s

CHzC12,18h m-

cCO2H

his-(sym-collidine) iodine(I) hex~~ophosphate Simonot, B.; Rousseau G, J. Org. Chem.,1993, 58,4

76% I

89%

Kitagawa, 0.; Inoue, T.; Hirano, K.; muchi.

T, J. Org. Cbem.,1993, 58, 3106

IQ, sodium persulfate, NaHC03 HOD Royer, AC.; Mebane, R.C.; Swafford, A.M. SynZett, 1993, 899

0

BzCl ,0.4 SmI3, MeCN , rt t

BzO/-I

0

Yu, Y.; m.

87% Y,; Ling, R. Synth. Commun., 1993, 23, 1973

*c

I

1. HC=CC02H, NC1 , CH2C12 2. (BzO), , PhH, eflux

Haaima,G.; Lunch, M.-J.; Routledge,A.; Wu

0

78~44%

0

Tetrahedron, 1993,49,4229

[email protected], DMSO BEt3, rt (opento air)

C02Et –

T

; Mu~gl~, E. Tetr~~~~r~~ Left., 1994, 35, 2763

I

54%

328

Compendiumof Organic Synthetic Methods, Vol9

BQ #

y-CO2H

H

1. mcpba

Section 359

ONlb2

2.12, NaHC03 50%

Reetz. MT,; Lauterbach,E.H. Heterocycles, 1993, 35, 627 Me

b.

X,; Wang, 2.; Ji, J. Tetrahedron Lett., 1994, 35, 613

Mimero, P.; Saluzzo, C.; m.

R, Tetrahedron Lett., 1996, 35, 1553

BeIIesia, F.; Boni, M.; Ghelfi. F,; Pagnoni, U.M. Tetrahedron L&t., 1994, 35, 2961 FzBr

Bu$nH , AIBN, PhH

t reflux , l-15 h addition ~ Meat ButtIe, L.A.; Motherwell. W.B, Tetrahedron Lett., 1994, 35, 3995 MeOg

Section 359

Ester – Halide

329

0 A Buoys

ma

c1

TBAB 190°C ) 6h S 97% K~ey~~

A.; Kiyota, M.;

Ph Y

0

T~tr~~~drun L&t., 1994, 35, 4571 Cl

AcCI , Cp2YCI w CH2C12, 13h

AcO ~

Ph

..

(88 ; Zhu, I), ~ynt~. ~~~~~.~

Cl

+

AC

Ph 12) 95%

1994, 24, 2203

I2 , Pb(OAc)za3 Hz0 , AcOH wrt ,6h 85% Bedekar, A.V.; Nair, K.B.; S~rn~n. R, ~ynt~. ~u~~~n., 1994,24, 2299 Br

PhMe3Nf Brf Ir Br

; G&in, R.H.; Musket,

GM.; Aionso, M.S. Tetr~~edrun, 1994, 50, 6433

Cl

Pimmg, F.O.H.; 1994,50, 12415

0.3 Cu(~py)C~ , DCE

57% (70:30) ; Kaptein, B.; Schoemaker, H.E. Tet~~~dr~~~

Compendiumof Organic Synthetic Methods, Vol9

330

00

, Zn , ether

0 w

25OC, 18h

Cl

Section 360

PhK

,///c’ 70%

Bhar, S.; &nu. BC, J. Org. Chem., 1995, 60, 745 SECTION

360: ESTER – KETONE 0 55%

1. Br

OH

Ktr

Br Py, ether Cd-f23 53% 2. TMSCl , ether cl lH23 Zn , reflux Landi Jr., J.J.; Garafalo, L.M.; &.mig. K, Tetrahedron Lett., 1993, 34, 277 COzMe

2% Rh2[02CCH(Bn)NPhth]4 C02Me

CO2Me CH2C12,O°C

d-

3S S bh

96%

(46%ee, R) Hashimoto, S.; Watanabe,N.; Sato,T.; Shiro, M.; Ikegami. S, Tetrahedron Lett., 1993, 34,

5109

x

Ph

1.7 PhI(OH)OTs , CDC13

-A rt ,2h 98% CO2Et C02Et Barton, D.H.R.: Jaszberenyi.J.Cs,; Shinada,T. Tetrahedron Lett., 1993, 34, 7191 PhCHO , EtN02 AlC13, 100°C, 5h

Sartori. (i; Bigi, E.; Maggi, R.; Bemardi, G.L. Tetrahedron Lett., 1993, 34, 7339

331

Ester – Ketone

section 360

Br

PhL

l-

, csgo3,

CH$& C02Et

48h, 30°C 2. aq. HCI, CHCI3 , Him-da, Y.; unhip,;

Tanaka, Y,; Ueda, I. J. Org. ~~~.,

1994, 59, 111

1. (Coa)2 , hv t

60%

2. MeOI-I

02Me ; Hardee, J.R.; Gelber, N.; Qi, L.; Axenmd, T. J. Org. Cbem., 1994, 59, 2131

ICI-I ) THF ,18-c-6 , rt

Me

4

60%

0

AC

Ph JL

OAc ,4% Pd(P~h3)2C12

Cl

w C7Hl K

SnBu3

Ph C7Hl

8% CuCN ,75”C, 18h

~

J, Am. Cam. Sot., 1994, 116, 1

Ye, J.; Bhatt, R.K.;

N c1

Ph -If

0

CO&B u

0

0

IsJr&o. B, Te&hedron

96%

L&t., 1994, 35, 5073

74%

0

332

Section 360

Compendium of Organic Synthetic Methods, Vol9

Me

Me

Mn(OAc), , AcOH 8O”C, 8h w

Me02C

0

C02Me 57%

C.-P,; Wang, S.-F. Tetrahedron Lett., 1994, 35, 4365 1, NaH , DME ,40°C 2. BuLi 3. PCC , Al203 , CHg12 93x68x68% Piers. E,; Cook, K.L.; Rogers, C. Tetrahedron Lett., 1994, 35, 8573 0 KMn04, CuSO&

Hz0 47%

4h * Das, J.; w

0

c

0

S, Tetrahedron, 1994, 50, 11709 e- , CH2C12- Hz0 NaBBr2

C02Me

C02Me 87%

Maekawa, H.; Ishino, Y.; mguchi. OH PhI-

L Chem. L&t., 1994, 1017

aq. t-B&OH, C02Et

1% CuC12,3% TBAB

CH2C12, 25OC, Id

*

PhA

C02Et 96%

Feldberg, L.; Sasson. Y, J. Chem. Sot. Chem. Commun., 1994, 1807

Section 360

Ester=Ketone

333

68% Ryu, 1; Nagahara,I(.; Yamazdci, H.; Tsunoi, S.; Sonoda. N, Synlett, 1994, 643

Xem Thêm :   đặc sản phố cổ hà nội

Bu$nH, AIBN

(9

m,

Kinter, KS. J. Org. Chem.,1995, 60, 4850 OCQMe

Xem Thêm :  Tóm tắt truyện Con Rồng cháu Tiên ngắn gọn nhất – lớp 6

Barba, I?.-

e’ , DMF/LiCIOd

0

67% h&G.: Montero. Cr..I. Org. Chem.,1995, 60, 5658 KMn04, pH 7 OEt

Tat‘iock. J,& J. org. Ckm, 1995,

C02t-B u

60,

OEt 0 97%

6221

1. CuBr2, PhI(OH)OTs , 0°C 2. DMAP .,dimethyldioxirane CH2C12,O”C

0 [email protected] 0

1st stepis quant Coats, S.J.; Wasserman.H.H, Tetrahedron Lett., 1995, 36, 7735

OPh

1.

J-I-IF

Li

PhCHO w;

Section 361

Com~n~um of Organic Synthetic Means, VoI 9

334

oAc

88~78%

2. p-TSA , A&H, 90°C , ld * PhA/ Yang, 2.; Moutou, J.-L. Tetrahedron Lett., 1995, 36, 841

l

–c Br

0

SmI2, THF , -35*C, 5 min

0

4 0

0

72%

d Park, H.S.; Lee, I.S.; I(im. YK

Tetrahedron Lett., 1995, 36, 1673

REVIEW:

“Alternate PreparationsOf aXeto EstersFrom Acid Chlorides,” &&i&&y. A,&; Wang, 2.; Wells, A.P. Org. Prep. Proceed. Int., 1995, 27, 457 AIso via ISetoacids Hydroxyketones

Section320 (Carboxylic Acid – Ketone) Section330 (Alcohol – Ketone)

SECTION 361: ESTER – NITRILE OAc I phwCHO

Nc Pdz(dba)&HQ , dppe MeCN, Id

Nemoto, H.; Kubota, Y.; Yamamoto. Y cJ. Chem. Sot. Chem. Commun., 1994, 1665

TBAF,THF,lh LiCI , rt

94% CN

Stojanova, D.S.; Milenkov, B.; Hesse.M, Helv. Chim. Acta, 1993, 76, 2303

Ester- Alkene

Section 362

335

ESTER – ALKENE

SECTION 362:

This sectioncontains synthesesof enol estersand estersof unsaturatedacidsas well asester moleculesbearing a remotealkenyl unit. 0

C02H

1. Br2, NaHC03 2. AgNOj , AcOH

Bu

Bu 66×50%

J&,&

T&; Huang, J. Tetrahedron Lett., 1993, 34, 1411 1. &CO3 ,5 kbar 2.5% Pd(OAc)z , 10% P(2-furyl)3

Jco2H

61%

3. HC=CCMe20Ac, DMSO 20°C , 14h ** Bouyssi, D.; Gore, J.; BaIme, G.; Louis, D.; Wallach, J. Tetrahedron L&t., 1993, 34, 3129 Me

90% Ciattini, P.G.; Mastropietro, G.; Morera, E.; Ortar, G, Tetrahedron Lett., 1993, 34, 3763

Ph-C=CH , NEt3, MeCN , rt 0 PdC12(PPh3)2 , CuI , 1Oh

*

Cu. X,; Huang, X.; Ma, S. Tetrahedron Lett., 1993, 34, 5963

Me$iCH=C=O , PhH OSiMe3

reflux ,3d

Me$iO Ito, T.; WT…

.

. ..

Me& T, Tetrahedron Lett., 1993, 34, 6583

P Ph

80% (>97:3 z:E)

336

Compendium of Organic Synthetic Methods, Vol9

a

[email protected]

Section 362

PBn [email protected]

I

MeN02, 80°C

0

65%

A

OBn

&lark& I.&; Evans, G.R. Tetrahedron tett., 1993, 34, 7309

c

Co-Cl2 [email protected]

(30

Me0 Et

..

70) 29% [60:40 E:zJ

Bhatia, B.; Reddy, M.M.; Iabal.

@Et

Tetrahedron L&t., 1993, 34,630l

1. SnC12 / 2.

=c_ ut.

CI-IO ,ether,rt >

F,; Gabriel, A.; Maillard, B.; Pereyre, M. Tetrahedron Lett., 1993, 34, 7749 cw

w bock.

5% Pd(OAc)z ,2 NaOAc DMSO , O2 )

am0

86%

RC,; Hightower, T.R. J. Org. Chem., 1993, 58, 5298 Bn

AcHN -A

1. PhSeCH$H20H, cw

Weinhouse, ML; Janda.

EDC

DMAP , DMF 2. [email protected], THF 3. iPr$H , CHCl3, reflux Synthesis, 1993, 8 1

Bn w AcHN

A

04 92×90%

Section 362

Ester – Alkene

337

+h

cCO2H

DMSO , Na2CO3 28-46h

70% Tetrahedron L&t., 1993, 34, 8545

Annby. U,; Stenkula, M.; -C.-M.

30%

;Jmco2Et

PPh3 7PhH , rt ,8h

Guo, C.; Lu.

.I. Chem. Sot. Chem. Commun., 1993, 394 Et0

OMe

CO2Me

,O.S Bu$nH E tog-

41% doMe

Lee. E,; Hur, CU.; I&e, 1466

,0.05 AIBN , reflux ,4h PhH (0.01 M) , syringe* pump v(2h)

C02Me Y.H.; Park, Y.C.; Kim, S.Y. .I. Chem. Sot. Chem. Commun., 1993,

P(OEt)3 , NEtyH20

,120OC –

C02Et

-COzEt

8h (sealed tube) 96%

Hirao. T,; Hiraw

K.; Ohshiro. Y, Bull. Chem.

TIN,

SOC.

Jpn., 1993, 66, 2781

MeOH,3MHCl 3-26h

Me0 Me0 Thakkar, K.; Cushman, M, Tetrahedron Lett., 1994, 35,644l

Section 362

Compendiumof Organic Synthetic Methods, Vol9

338

Pd(OAc)z , dppp , PhMe , MeOH w COzMe reflux

Mand;u. TJ Tsujiguchi, Y.; Tsuji, J.; Saito, S. Tetrahedron Lett., 1994, 35, 5701 Bu [Pd(MeCN)2(p&)d @=I12 co, THE;, 5o”c (10 Kg cms2)

‘b O

0

+Bux; 2

.

83) 92% Y, Tetrahedron Lett., ;994, 35, 5889

(17

Matsushita, K.; Komori, T.; Oi, S.; w.

l.NaI-I,TMEDA,THF,reflux 2. inverse addition to PhOCOCl

0a

OPh 43%

Harwood, L.M.; Houminer, Y.; Manage, A.; Seeman.J-1,Tetrahedron Lett., 1994, 35, 8027

eC02Me PhCHO

*

phL-oH

34%

DABCO , microwave, 10 min CO2Me Kundu, M.K.; Mulcherjee, S.B.; Balu, N.; Padmakumar,R.; I$&& S.V,Synlett, 1994,444 BrCHzCOfle , Bu3As , 10% Cd PhCHO

100°C ,20h

Zheng, J.; ahen, Y, Synth. Commun., 1994, 24, 2069

*

PhwC02Me 87% (E only)

Nz

)I

339

Ester – Alkene

Section 362

Lf Rh2(s-TBSP)4

CO2Me

p-(t-butyl)phenylsulfonyl prolinate 76% (63% ee) . TBSP = Peng, ava; Z-Q.; Houser, J.H. Tetrahedron Lett., 1994, 35, 8939 Mac

,3.5% Pd(OAc)z 8% PPh3 , 1.2 Ag2CQ , MeCN 90°C, 45 min 80%

Meyer, F.E.; Ang, K.H.; Stenig, A.G.; de Meijere, A. Synlett, 1994, 191 -0Ac

, CO, THF , autoclave

RuC12(PPh3)3-K2C03, 2OOOC, 77%

Kondo, T.; Kodoi, K.; Mitsudo, T.-u.; Watanabe.Y t J. Chem. Sot. Chem. Comnun., 1994, 755

1. Rieke Mg* , THF , rt 2. ethylene oxide ) THF , -78OC v

a

3.co;!,o”c + rt 4. H30+, 1lOC

Rieke. R.D; Sell, MS.; Xiong, H. J. Org. Chem., 1995, 60, 5143 Me0

nBu3 SPh

cu(No3)2

Ph

9m 9fi

CO2Me 65%

TV

CO2Me SPh Beddoes,R.L.; Cheeseright,T.; Wang, J.; Quayle. P, Tetrahedron Lett., 1995, 36, 283

340

Compendiumof Organic Synthetic Methods,Vo19

Section 362

COzMe Ph3A

CO2Me

4

SePh

PhCHO

*

CHC13,4h Huang, Z.-Z.; Huane,

4

SePh Y. -7* Tetrahedron Lett., 1995, 36,425

.

-F C3H7

96% (90:10, Z-E)

PhH

w7

Ph

I

5% ClzPd(PPh3h.4 NEt3 20atmC0,PhH,l10°C,10h

0

99%

Cop&et, C.; Sugihara, T.; Wu, G.; Shimoyama,I.; Negishi. E, J. Am. Chem. Sot., 1995, 117, 3422 -cl

; NEI+;IH2C12,-20°C

a *

.

0

w.

.

OBn 75%

G,; De Simone, A.; Mingardi, A.; Tomasini, C. Synlett, 1995, 1131

3) 95%

(>97

Zhu, G.; Lu. X, Tetrahedron Asymmetry, 1995, 6, 345 m PhO

Cl

SiMe3 , toluene AlC13, 20°C ,2h

PhOL 82%

Mayr. H,; Gabriel, A.O.; Schumacher,R. Liebigs Ann. Chem., 1995, 1583

Section 363

osMe3

OPl

. m.

341

Ether – Ether

M+C

COzMe

zrC14,Cc4,0°c

~

pflzc

+ rt

Mew . &, Sudoh, T.; Koyama, K. Bull. Chem. Sot. J’n., 1995,68, 1683 RelatedMethods: Also via Acetylenic Esters: Alkenyl Acids: P-Hydroxy-esters:

SECTION 363:

80%

Section60A (Protectionof Aldehydes). Section 180A (Protectionof Ketones). Section 306 (Alkyne – Ester). Section322 (Carboxylic Acid – Alkene). Section 327 (Alcohol – Ester).

ETHER, EPOXIDE, THIOETHER EPOXIDE, THIOETHER

– ETHER,

SeeSection60A (Protectionof Aldehydes)and Section 180A (Protectionof Ketones)for reactionsinvolving formation of Acetalsand Ketals. 1. DDQ , MeOH , CH2C12 rt, Id 2. aq. NaHC03 OMe &I. Y.-C,; Lebeau,E.; Gillard, J.W.; Attardo, G. Tetrahedron L&t., 1993, 34, 3841

4 /

H

iPrOH ,20% CuC12 5% Pd(N0)2C1(MeCN)2 2h

50% isolated Meulemans,T.M.; Kiers, N.H.; FeringZLR.L; van Leeuwen, P.W.N.M. Tetrahedron L&t., 1994, 35, 455

HO

DEAD, PPh3, CHg12, O°C HO OH

80% @-only) Sobti, A.; Sulikowski. G.A, Tetrahedron L&t., 1994, 35, 3661

78%

Section 364

Compendiumof Organic Synthetic Methods, Vol9

342

(a$ = 1:15) 81% BTIB = his-(trifluoroacetoxy)idobenzene Sun, L.; Li, P.; Zhao. K, Tetrahedron Lett., 1994, 35, 7147 TMS-SPh , DMF w

‘OMe ;w”l

Miura, T.; w.

0

87%

Y, Tetrahedron Lett., 1994, 35, 7961 OSiMqt-Bu Q = 2 s

OMe

t

ZnI2 , THF

p-To1

70% (>99% e) Kita. Y,; Shibata, N.; Fukui, S.; Fujita, S. Tetrahedron Lett., 1994, 3.5, 9733

ETHER, EPOXIDE, THIOETHER SULFONATE

SECTION 364:

1. ClCH21, MeLi , -78°C ‘Ls 2. -78OC +

+20°c

Br Barluenu;

– HALIDE,

Me4N*#,,,, ,,+,Me 62% $

Cl

Llavona, L.; Bemad, P.L.; Concellbn, J.M. Tetrahedron Lett., 1993, 34, 3173 H

XeF2

, CH2C12,35OC

Stavber, S.; Zupan, M. Tetrahedron Lett., 1993, 34,4355

Section 364

Ether – Halide

343

MnO2, AcCl w Cl 82% Bellesia, F.; Ghelfi, F.; Pagnoni, U.M.; Pinetti. A, GQzz.Chim. Ital., 1993, 123, 289

t(

OMe

OMe

Br2, Me&Cl, NaBr ,30 min B *

OMe

3-(

OMe 98%

Bell&a, F.; Boni, M.; Ghelfi.;

Pagnoni, U.M. Gazz. Chim. Ital., 1993, 123, 629

60% Antonioletti, R.; Magnanti, S.; Screttri, A. Tetrahedron Lett., 1994, 35, 2619 l.LDA,HMPA 2. acetone 3. X2,NaHC03

32×47% Galatsis. P,; Parks,D.J. Tetrahedron L&t., 1994, 35, 6611 H ,,OH @9

,,\I”l

12, NaHC03 , dry MeCN

IIIIIIIIB u

Bu 16h 04

*

d-J

r,e % -1

75% Barks, J.M.; Knight. D.W,; Weingarten, G.G. J. Chem. Sot. Chem. Commun., 1994, 719 PhI(&~F3)2

9t t 12 cc14

D’Auria, M.; Mauriello, G. Tetrahedron Lett., 1995, 36,4883

83% I

Section 365

Compendiumof Organic Synthetic Methods, Vol9

344

AK13 , Id

.

(4 s

1) 60%

J.0,; Biermann, U. Bull. Sot. Chim. Be&., 1994, 10, 393

CT I

(collidine)$ PFi t

A//

0

CH2Cl2

95%

Brunel, Y .; Rousseau,G. Synlett, 1995, 323

&

12, CAN, MeOH *

rt ,2h

I*

+

I

.

I

1) 88% (2 6 ; Hosokawa,H.; Kanamori, M.; Muramatsu, Y.; bhiai, K.; Takahashi,E. Chem. Lett., 1995, 13 .

.

SECTION

365:

ETHER,

EPOXIDE,

THIOETHER

– KETONE Me

‘OSiMe3

0

OH

BFpOEt2, MeN02, -25OC 30 min

?Y-

51%

(7:3 syn:anti)

Duhamel. P,; Guillemont, J.; Poirier, J.-M. Tetrahedron Lett., 1993, 34, 4197 2% Cu(hfacac)z, CH2C12 40%

reflux *

c

hfacac = hexafluoroacetyl acetonate Clark. J.S; Krowiak, S.A.; Street,L.J. Tetrahedron Lett., 1993, 34,4385

Section 365

Ether – Ketone

345

%

M

2Me:3Me) I

I 0

M&, Rivera-Fortin, M.A.; Byrne, N.E. Tetrahedron Lett., 1993, 34, 3505 Ph, t-Bu

, Me2AICl

A-

,,,,,d Ph

SPh

CH2C12,-45OC

(96:4) where 4 = other isomers Horiguchi, Y.; Suehiro, I.; Sasaki,A.; Kuwaiima, I, Tetrahedron Lett., 1993, 34, 6077 Me Me

TMS zc

I cf

5% TMSN(S02F)2 CH2C12,-78OC

Trehan, A.; Vij, A.; Walia, M.; Kaur, G.; Veu.. 7335

0

p-TsOH , H20, CH& 20°C, 12h Cossy. J,; Furet, N. Tetrahedron Lett., 1993, 34, 7755

&r

. Treh;iB. S, Tetrahedron Lett., 1993, 34,

*

SePh 70%

346

Section 365

Compendiumof Organic Synthetic Methods, Vol9

5

[mCl(C2H4)d

2 9 SnC12

acetone, Ar , 80°C

P

sealedtube, 1Oh

-* Tetrahedron Let?., 1993, 34, 7971

Ipatkin, V.V.; Kovalev, I.P.; Ignatenko, A.V.; Nikishin.,

C02Me TrSbC16,CH$12 ,-78’C (>2OO:1)

76%

Colander. GA; Cameron,K.O. J. Org. Chem., 1993, 58, 5931

M%* ,,+ (‘I

Al(OC&)3 , toluene O°C,2h

0

) o2

%

Me Ishihm, K.; Han&i, N.; Yamamoto, H. Synlett, 1993, 127 w-h1

0

= Z = Z

Me

Me

Me

>99% (86:14 S:R)

63% Groth, U,; Huhn, T.; Richter, N. Liebigs Ann. Chem., 1993, 49 OH MeCHO , PhSH , CH-& SiO2 , rt Fuchs, K.; m.

I&

J. Org. Chem., 1994, 59, 528

SPh

Section 365

Ether – Ketone

347

OEt C5Hdy 66%

O

PCWP = peroxotungstophosphate Sakaguchi,S.; Watase,S.; Katayama,Y.; Sakata,Y.; Nishiyama, Y.; I&ii. Y c.I. Org. Chem., 1994, 59, 5681 N-NHCO$t

7/

Me

1. Br2 3. 2. MeOH, NaHC03H+ 4. H30+

*

+

0

5. DBU 77%

Feuerer, A.; Sevea T, J. Org. Chem., 1994, 59, 6026 Ph k== TMSO

3 eq. SnC4, -78OC,CH$l;! *

PhbSPh

67% m.

k; Michael, J.P.; Walter, D.S. Tetrahedron Let&, 1994, 35, 5481 (~-To~)~S~, cat. Ph2CO , Yb rt ,3h

. . Tanlguchl. Y,; Maruo, M.; mi.

STolyl IL; Fuiiwara. Y, Tetrahedron Lett., 1994, 35, 7789

KF-Al203 , t-B&OH, Pha ~v.K.;

Ph

0 CH2C12

MeCN , 10 min

Ph

5, PhI>K 0

quant

Kapoor, K.K. Tetrahedron Lett., 1994, 35,948l 0

1. NBS, (BzO)2, CC4, heat 56% +

2.1.5 Ag2C03 , MeOH , heat

Me0 . Cl m. N,; Stanoeva,E.; Boeykens,M. Synthesis, 1994,427

OMe

Compendiumof Organic Synthetic Methods, Vo19

348

Section 365

1. EtCH(OMe)z , TiCL4 ;~lz,-780C,lh

EtzNqms2

.

2

quant. 0 Hojo, M.; Nagoyoshi, M.; Fujii, A.; Yanagi, T.; Ishibashi, N.; Miura, K.; Hosomi. A, Own. Lett., 1994, 719

OH

W-h

2

4

OAc

9 CH2Cl2

2 snCl;!,2 NCS , -1O’C 80% (40x50synxznti) Masuyama. Y,; Kobayashi, Y.; Kurusu, Y. J. Chem. Sot. Chem. Commun., 1994, 1123

4f

CO2Me

3e4*

>

Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)Compendium of Organic Synthetic MethodsCompendium of Organic Synthetic Methods Volume 9 MICHAELB. SMITHDEPARTMENT OF CHEMISTRY THE UNIVERSITY OF CONNECTICUT STORRS, CONNECTICUTA Wiley-IntersciencePublicationJOHN WILEY & SONS, INC. New YorkChichesterWeinheimBrisbaneSinaar>oreTorontoCopyright  2001 by John Wiley and Sons, Inc., New York. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic or mechanical, including uploading, downloading, printing, decompiling, recording or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without the prior written permission of the Publisher. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-Mail: PERMREQ @ WILEY.COM. This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold with the understanding that the publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional person should be sought. ISBN 0-471-22822-2. This title is also available in print as ISBN 0-471-14579-3. For more information about Wiley products, visit our web site at www.Wiley.com.Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)CONTENTS PREFACE ABBREVIATIONS INDEX, MONOFUNCTIONAL COMPOUNDS INDEX, DIFUNCTIONAL COMPOUNDS INTRODUCTION PREPARATION OF ALKYNES PREPARATION OF ACID DERIVATIVES PREPARATION OF ALCOHOLS PREPARATON OF ALDEHYDES PREPARATION OF ALKYLS, METHYLENES AND ARYLS PREPARATION OF AMIDES PREPARATION OF AMINES PREPARATION OF ESTERS PREPARATION OF ETHERS, EPOXIDES AND THIOETHERS 10 PREPARATION OF HALIDES AND SULFONATES 11 PREPARATION OF HYDRIDES 12 PREPARATION OF KETONES 13 PREPARATION OF NITRILES 14 PREPARATION OF ALKENES 15 PREPARATION OF OXIDES 16 PREPARATION OF DIFUNCTIONAL COMPOUNDS AUTHOR INDEXvii ix … XIIIxv1 5 11 48 58 100 117 140 156 171 176 183 208 212 227 235 391PREFACE Since the original volume in this series by Ian and Shuyen Harrison, the goal of the Compendium of Organic Synthetic Methods was to facilitate the search for functional group transformations in the original Iiterrature of Organic Chemistry. In Volume 2, difunctional compounds were added and this compilation was continued by Louis Hegedus and Leroy Wade for Voume 3 of the series. Wade became the author for Volume 4 and continued with Volume 5. I began editing the series with Volume 6, where I introduced an author index for the first time and added a new chapter (Chapter 15, Oxides). Volume 7 introduced Sections 378 (Oxides-Alkynes) through Section 390 (Oxides-Oxides). The Compendium is a handy desktop reference that will remain a valuable tool to the working Organic chemist, allowing a “quick check” of the literature. It also allows one to “browse” for new reactions and transformations that may be of interest. The body of Organic literature is very large and the Compendium is a focused and highly representative review of the literature and is offered in that context. Compendium of Organic Synthetic Methods, Volume 9 contains both functional group transformations and carbon-carbon bond forming reactions from the literature appearing in the years 1993, 1994 and 1995. The classification schemes used for volumes 6-8 have been continued. Difunctional compounds appear in Chapter 16. The experienced user of the Compendium will require no special insructions for the use of Volume 9. Author citations and the Author Index have been continued as in Volumes 6-8. Every effort has been made to keep the manuscript error free. Where there are errors I take full responsibility. If there are questions or comments, the reader is encouraged to contact me directly at the address, phone, fax, or Email addresses given below. As I have througout my writing career, I thank my wife Sarah and my son Steven who have shown unfailing patience and devotion during this work. I also thank Darla Henderson, the editor of this volume. MichaelB. SmithDepartment of Chemistry University of Connecticut 55 N. Eagleville Road Storrs, Connecticut 06269-3060 Voice phone: (860)-486-2881 Fax: (860)-486-2981 Email: smith @Inucleus.chem.unconn.eduviiABBREVIATIONS 0 ACAcetylacac AIBN aq*Acetylacetonate azo-bis-isobutyronitrile AqueousCH39-Borabicyclo[3.3.1]nonylborylB99-BBN BER BINAP Bn Bz9-Borabicyclo[3.3.1]nonane Borohydride exchange resin 2R,3S-2,2’-bis-(diphenylphosphino)-1,lr-binapthyl benzyl benzoylBOCt-ButoxycarbonylOt-BuBu CAM CAN ccat.2,2’-Bipyridyl n-Butyl Carboxamidomethyl Ceric ammonium nitrate cycloCatalyticCbzCarbobenzyloxyChirald COD COT CP CSA CTAB2S,3R-(+)-4-dimethylamino1,2-diphenyl-3-methylbutan-2-01 1$Cyclooctadienyl 1,3,5cyclooctatrienyl Cyclopentadienyl Camphorsulfonic acid Cl&I33NMe3+Brcetyltrimethylammonium bromidebPY WPY)CY (+jH OC DABCO dba DBE DBN DBU DCC11)Cyclohexyl Temperature in Degrees Centigrade 1,4-Diazobicyclo[2.2.2]octane dibenzylidene acetone 1,2-Dibromoethane 1,8-Diazabicyclo[5.4.0]undec-7-ene 1,5-Diazabicyclo[4,3,O]non-5-ene 1,3-Dicyclohexylcarbodiimide-CH2CH2CH2CH3 (NH)2Ce(NO3)6 0 &OCH2Ph+oBrCH2CH2Brc-C6H13-N=C=N-c-C6H13 ixDCEABBREVIATIONS% de DEA DEAD Dibal-H Diphos (dppe) Diphos-4 (dppb) DMAP DMA DME1,2-Dichloroethane 2, 3-Dichloro-5,6-dicyano1,4-benzoquinone % Diasteromeric excess Diethylamine Diethylazodicarboxylate Diisobutylaluminum hydride 1,2-bis-(Diphenylphosphino)ethane 1,4-his-(Diphenylphosphino)butane 4-Dimethylaminopyridine Dimethylacetamide DimethoxyethaneDMFN,N’-DimethylformamideDDQC1CH2CH2ClHN(CH2CH3)2 Et02C-N=NC02Et (Me2CHCH2)2AlH Ph2PCH2CH2PPh2 Ph2P(CH2)4PPh2MeOCH2CH20Me 0 Hdmp dpm dPPb dPPe dPPf dPPP dvb e% ee EE Et EDA EDTA FMN fod FP FVP h hv 1,5-HD HMPA HMPT iPr LICA (LIPCA) LDA LHMDS LTMP MABR MAD mCPBA Me MEM MesK N(CH3)2bis-[ 1, [email protected] )1,3-propanedionato] dipivaloylmethanato 1,4-bis-(Diphenylphosphino)butane Ph2P(CH2)4PPh2 1,2-bis-(Diphenylphosphino)ethane Ph2PCH2CH2PPh2 bis-(Diphenylphosphino)ferrocene 1,3-bis-(Diphenylphosphino)propane Ph2P(CH2)3PPh2 Divinylbenzene Electrolysis % Enantiomeric excess EtO(Me)HCO1-Ethoxyethyl -CH2CH3 Ethyl H2NCH2CH2NH2 Ethylenediamine Ethylenediaminetetraacetic acid Flavin mononucleotide tris-(6,6,7,7,8,8,8)-Heptafluoro-2,2-dimethyl-3,5-octanedionate Cyclopentadienyl-bis-carbonyl iron Flash Vacuum Pyrolysis hour (hours) Irradiation with light 1&Hexadienyl (Me3N)3P=O Hexamethylphosphoramide Hexamethylphosphorous triamide (Me3N)3P Isopropyl -CH(CH3)2 Lithium cyclohexylisopropylamide LiN(iPr)2 Lithium diisopropylamide LiN(SiMe3)2 Lithium hexamethyl disilazide Lithium 2,2,6,6-tetramethylpiperidide Methylaluminum bis-(4-bromo-2,6-di-tert-butylphenoxide) bis-(2,6-di-t-butyl-4-methylphenoxy)methyl aluminum meta-Chloroperoxybenzoic acid Methyl -CH3 MeOCH2CH20CH2P-Methoxyethoxymethyl 2,4,6-tri-Me-C6H2 MesitylABBREVIATIONSMeOCH2CH3SO2-MOM MS MS MTM NAD NADP Napth NBD NBS NCS NIS Ni(R) NMP OxoneMethoxymethyl Methanesulfonyl Molecular Sieves (3Aor 483 Methylthiomethyl Nicotinamide adenine dinucleotide Sodium triphosphopyridine nucleotide Napthy CC1oH$ Norbornadiene N-Bromosuccinimide N-Chlorosuccinimide N-Iodosuccinimide Raney nickel N-Methyl-2-pyrrolidinone 2 KHS05.KHS04aK2S040PPolymeric backbonePCC PDC PEGPyridinium chlorochromate Pyridinium dichromate Polyethylene glycolPhPhenylPhH PhMe Phth pitBenzene Toluene Phthaloyl 2-PyridinecarboxylatePipPiperidinePMP4-methoxyphenylPrn-Propyl-CH2CH2CH3PYPyridineN- / 3quant. Red-Al sBu sBuLi Siamyl TADDOI TASF TBAF TBDMS TBHP (t-BuOOH) t-Bu TEBA TEMPOQuantitative yield [(MeOCH2CH20)2AlH2]Na set-Butyl set-Butyllithium Diisoamyl a,a,a’,a’-tetraaryl-4,5-dimethoxy-1,3-dioxolane tris-(Diethylamino)sulfonium difluorotrimethyl Tetrabutylammonium fluoride t-Butyldimethylsilyl t-Butylhydroperoxide tert-B utyl Triethylbenzylammonium Tetramethylpiperdinyloxy free radicalCH3SCH2-to/ H-NCH3CH2CH(CH3) CH3CH2CH(Li)CH3 (CH3)2CHCH(CH3)silicate n-Bu4N+F t-BuMe2Si Me3COOH -C(CH3)3 Bn(CH3)3N+ABBREVIATIONSxiiTFA TFAA Tf (OTf) THF THP TMEDA TMG TMS TMP TPAP To1 Tr TRIS Ts(Tos)Trifluoroacetic acid Trifluoroacetic anhydride Triflate Tetrahydrofuran Tetrahydropyran Tetramethylethylenediamine 1,1,3,3-Tetramethylguanidine Trimethylsilyl 2,2,6,6-Tetramethylpiperidine tetra-n-Propylammonium perruthenate Tolyl Trityl Triisopropylphenylsulfonyl Tosyl = p-ToluenesulfonylN),,)SonicationxcChiral auxiliaryCF3COOH (CF3CO)20 -S02CF3(-OS02CF3)Me2NCH2CH2NMe2 -Si(CH3)34-c#&H3 -CPh3 4-Mec6&INDEX,MONOFUNCTIONALCOMPOUNDSSections–heavy type Pages–light type Blanks in the table correspond to sections for which no additional examples were found in the literatureSect. Carboxylic Alcohols, Aldehydesacids phenolsAmideS AIIli~SKetonesPREPARATIONPg.30A 45A 60A 90A 105A 180A9 f: 115 137 206OF ‘lFROMAlkynesCatboxylic derivatives Alcohols,1 1acid phenols31 11Aldehydes Alkyls, methylenes, aryls Amid=17 518 619 632 1133 1234 1347 4848 4849 49Ethers, epxoides Halides,63646560606176 loo77 100106 140107 140121 156 137 171166 183167 184Nitriles Alkenes Miscellaneous78 10180 10252 5198 12999 129113 146114 148109 144111 145123 156124 158128 159 140 172184 208 199 2171% 212197 216198 217211 227212 227213 227171 191172 192186 209 200 219201 220ml 178 173 19312 314 315 325 727 829 830 944 3945 4140 2941 3055 52 70 65129 160159 179 174 193188 20971 70203 220204 221217 228218 228219 22859 5470 5587888990 112 113113113103 132104 132105 133118 15372 71101130131102 131116 150117 151115 149 130 161131 161132 161145 173146 173147 174160 179 175 195162 181 176 1%119 154 134 162 149 175163 182177 198179 202222 232135 169 150 175180 204 1% 211207 223 221 232120 154165 182192 21020s 221 220 23243 39 58 53loo1% 209202 22042 30 57 5385 111142 172 157 177170 19169 6597 120108 142la3 20854 5283 11096 119169 18953 5182 10894 118168 18639 2681 10293 117138 17124 738 2668 64153 176(RH) Ketones50 5061sulfonatesHydrides36 2558Amines Esters23 710 2223 233209 223210 225234 233225 233*.. XIIIINDEX, Sections-heavyDIFUNCTIONALCOMPOUNDStypePages-light typeBlanks in the table correspond to sections for which no additional examples wem found in the literature305 337316 242326 252335 283343 288307 238318 243328 261337 284345 290309 239320 244310 239311 239 378xiv322 244352 309358 325363 340359364330 267347 293354 312340 330365 344331 274348 296355 315361 334366 350332 276341 284349 296356362367380381382383384385368386INTRODUCTION Relationship between Volume 9 and Previous Volumes. Compendium of Organic Synthetic Methods, Volume 9 presents about 1200 examples of published reactions for the preparation of monofunctional compounds, updating the 10650 in Volumes l-8. Volume 9 contains about 800 examples of reactions which prepare of difunctional compounds with various functional groups. Reviews have long been a feature of this series and Volume 9 adds almost 90 pertinent reviews in the various sections. Volume 9 contains approximately 1000 fewer entries than Volume 8 for an identical three-year period, primarily for difunctional compunds. Interestingly, there are about 500 fewer citations from the most cited journal (Tetrahedron Letters) than in the previous edition. Whether this represents a trend in the literature or an inadvertent selectivity on my part is unknown, but there has been a clear increase in biochemical and total synthesis papers which may account for this. Chapters l-l 4 continue as in Volumes l-8, as does Chapter 15, introduced in Volume 6. Difunctional compounds appear in Chapter 16, as in Volumes 6 and 7. The sections on oxides as part of difunctional compounds, introduced in Volume 7, continues in Chapter 16 of Volumes 8 and 9 with Sections 378 (Oxides-Alkynes) through Section 390 (Oxides-Oxides). Following Chapter 16 is a complete alphabetical listing of all authors (last name, initials). The authors for each citation appear below the reaction. The principle author is indicated by underlining (i.e., Kwon, T.W.; Smith, M. B.), as in Volumes 7 and 8. Classification and Organization of Reactions Forming Monofunctional Compounds. Chemical transformations are classified according to the reacting functional group of the starting material and the functional group formed. Those reactions that give products with the same functional group form a chapter. The reactions in each chapter are further classified into sections on the basis of the functional group of the starting material. Within each section, reactions are loosely arranged in ascending order of year cited (1993-1995), although an effort has been made to put similar reactions together when possible. Review articles are collected at the end of each appropriate section. The classification is unaffected by allylic, vinylic, or acetylenic unsaturation appearing in both starting material and product, or by increases or decreases in the length of carbon chains; for example, the reactions t-BuOH PhCOOH, and PhCH=CHCH20H t-BuCOOH, PhCH20H PhCH=CHCOOH would all be considered as preparations of carboxylic acids from alcohols. Conjugate reduction and alkylation of unsaturated xvxviINTRODUCTIONketones, aldehydes, esters, acids, and nitriles have been placed in Sections 740 and 74E (Alkyls from Alkenes), respectively. The terms hydrides, alkyls, and aryls classify compounds containing reacting hydrogens, alkyl groups, and aryl groups, respectively; for example, RCH2-H – RCH2COOH (carboxylic acids from hydrides), RMe – RCOOH (carboxylic acids from alkyls), RPh – RCOOH (carboxylic acids from aryls). Note the distinction between R2CO – R2CH2 (methylenes from ketones) and RCOR’ – RH (hydrides from ketones). Alkylations involving additions across double bonds are found in Section 74 (alkyls, methylenes, and aryls from alkenes). The following examples illustrate the classfication of some potentially confusing cases: RCH=CHCOOH RCH=CH2 ArH ArH RCHO RCH=CHCHO RCHO R2CH2 RCH2COR RCH=CH2- RCH=CH2 – RCH=CHCOOH – ArCOOH – ArOAc – RH – RCH=CH2 – RCH3 – R2C0 – R2CHCOR – RCH2CH3RBr + HC-CHRCH-CRROH + RCOOHRCOORRCH=CHCHORCH2CH2CH0RCH=CHCNRCH2CH2CNHydrides from carboxylic acids Carboxylic acids from hydrides Carboxylic acids from hydrides Esters from hydrides Hydrides from aldehydes Hydrides from aldehydes Alkyls from aldehydes Ketones from methylenes Ketones from ketones Alkyls from alkenes (Hydrogenation of Alkenes) Alkynes from halides; also al kynes from al kynes Esters from alcohols; also esters from carboxylic acids Alkyls from alkenes (Conjugate Reduction) Alkyls from alkenes (Conjugate Rduction)How to Use the Book to Locate Examples of the Preparation of Protection Examples of the preparation of one funcof Monofunctional Compounds. tional group from another are found in the monofunctional index on p. x, which lists the corresponding section and page. Sections that contain examples of the reactions of a functional group are found in the horizontal rows of this index. Section 1 gives examples of the reactions of alkynes that form new alkynes; Section 16 gives reactions of alkynes that form carboxylic acids; and Section 31 gives reactions of alkynes that form alcohols. Examples of alkylation, dealkylation, homologation, isomerization, and transposition are found in Sections 1, 17, 33, and so on, lying close to a diagonal of the index. These sections correspond to such topics as the preparation of alkynes from alkynes; carboxylic acids from carboxylic acids; andINTRODUCTIONxviialcohols, thiols, and phenols from alcohols, thiols, and phenols. Alkylations that involve conjugate additions across a double bond are found in Section 74E (Alkyls, Methylenes, and Aryls from Alkenes). Examples of name reactions can be found by first considering the nature of the starting material and product. The Wittig reaction, for instance, is in Section 199 (Alkenes from Aldehydes) and Section 207 (Alkenes frorm Ketones). The aldol condensation can be found in the chapters on difunctional compounds in Section 324 (Alcohol, Thiol-Aldehyde) and in Section 330 (Alcohol, Thiol-Ketone). Examples of the protection of alkynes, carboxylic acids, alcohols, phenols, aldehydes, amides, amines, esters, ketones, and alkenes are also indexed on p. xvii. Section (designated with an A: 15A, 30A, etc.) with “protecting group: reactions are located at the end of pertinent chapters. Some pairs of functional groups such as alcohol, ester; carboxylic acid, ester; amine, amide; and carboxylic acid, amide can be interconverted by simple reactions. When a member of these groups is the desired product or starting material, the other member should also be consulted in the text. The original literature must be used to determine the generality of reactions, although this is occasionally stated in the citation. This is only done in cases where such generality is stated clearly in the original citation. A reaction given in this book for a primary aliphatic substrate may also be applicable to tertiary or aromatic compounds. This book provides very limited experimental conditions or precautions and the reader is referred to the original literature before attempting a reaction. In no instance should a citation inthis book be taken as a complete experimental procedure. Failure to refer to the original literature prior to beginning laboratory work could be hazardous. The original papers usually yield a further set of references to previous work. Papers that appear after those publications can usually be found by consulting Chemical Abstracts and the Science Citation Index.Classification Compounds.and Organizationof ReactionsFormingDifunctionalThis chapter considers all possible difunctional compounds formed from the groups acetylene, carboxylic acid, alcohol, thiol, aldehyde, amide, amine, ester, ether, epoxide, thioether, halide, ketone, nitrile, and alkene. Reactions that form difunctional compounds are classified into sections on the basis of two functional grups in the product that are pertinent to the reaction. The relative positions of the groups do not affect the classification. Thus preparations of 1,2=amino=alcohols, 1,3-amino-alcohols, and 1,4amino-alcohols are included in a single section (Section 326, AlcoholAmine). Difunctional compounds that have an oxide as the second group are found in the appropriate section (Sections 278-290). The nitroketone product of oxidation of a nitroalcohol is found in Section 386 (Ketone-Oxide). Conversion of an oxide to another functional grup is generally found in the “Miscellaneous” section of the sections concerning monofunctional com-.. . XVIIIINTRODUCTIONpounds. Conversion of a nitroalkane to an amine, for example is found in Section 105 (Amines from Miscellaneous Compounds). The following examples illustrate applications of this classification system: Difunctionaf Product RGC-C-CR RCH(OH)COOH RCH=CHOMe RCHF2 RCH(Br)CHzF RCH(OAc)CH20H RCH(OH)COzMe RCH=CHCH2C02Me RCH=CHOAc RCH(OMe)CH2SO2CH$H2OH RS02CH2CH20HSection Et/e Alkyne-Alkyne Carboxylic acid-Alcohol Ether-Alkene Halide-Halide Halide-Halide Alcohol-Ester Alcohol-Ester Ester-Alkene Ester-Alkene Alcohol-Ether Alcohol-OxideHow to Use the Book to Locate Examples of the Preparation of Difunctional Compounds. The difunctional index on pWxi gives the section and page corresponding to each difunctional product. Thus Section 327 (Alcohol, ThiolEster) contains examples of the preparation of hydroxyesters; Section 323 (Alcohol, Thiol-Alcohol, Thiol) contains examples of the preparation of diols. Some preparations of alkene and acetylenic compounds from alkene and acetylenic starting materials can, in principle, be classified in either the monofunctional or difunctional sections; for example, the transformation RCH=CHBr – RCH=CHCOOH could be considered as preparing carcompounds) or boxylic acids from halides (Section 25, monofunctional preparing a carboxylic acid-alkene (Section 322, difunctional compounds). The choice usually depends on the focus of the particular paper where this reaction was found. In such cases both sections should be consulted. Reactions applicable to both aldehyde and ketone starting materials are in many cases illustrated by an example that uses only one of them. Likewise, many citations for reactions found in the Aldehyde-X sections, will include examples that could be placed in the Ketone-X section. Again the choice is dictated by the paper where the reaction was found. Many literature preparations of difunctional compounds are extensions of the methods applicable to monofunctional compounds. As an example, the reaction RCI – ROH might be used for the preparation of diols from an appropriate dichloro compund. Such methods are difficult to categorize and may be found in either the monofunctional or difunctional sections, depending on the focus of the original paper. The user should bear in mind that the pairs of functional groups alcohol, ester; carboxylic acids, ester; amine, amide; and carboxylic acid, amide can be interconverted by simple reactions. Compounds of the typeINTRODUCTIONxixRCH(OAc)CH20Ac (ester-ester) would thus be of interest to anyone preparing the diol RCH(OH)CH20H (alcohol-alcohol). Sources of Literature Citations. I thought it would be useful for a reader of this Compendium to see the distribution of citations used to this book (i.e., which journals have the most new synthetic methodology). As seen in the accompanying graph, Tetrahedron Letters and Journal of Organic Chemistry account for roughly 60% of all the citations in Volume 9. This book was not edited to favor one journal, category or type of article over another. Undoubtedly, my own personal preferences are part of the selection but I believe that this compilation is an accurate represention of new synthetic methods that appear in the literature for this period. Therefore, I believe the accompanying graph reflects those journals where new synthetic methodology is located. I should point out that the category “18 other journals” includes: Accts. Chem. Res.; Acta Chem. Stand.; Angew. Chem. Int. Ed. Engl.; Bull. Chim. Sot. Be/g.; Bull. Chim. Sot. Fr.; Can. J. Chem.; Chem. Ber.; Gazz. Chim. Ital.; Heterocycles; J. Chem. Sot.; J. Het. Chem.; J. Indian Chem. Sot; Liebigs Ann. Chem.; Org. Prep. Proceed Int.; Reel. Tram. Chim., Pays-Bas; and Tetrahedron Asymmetry. In addition, nine more journals were examined but no references were recorded.18 other journalsKS Perkin ITetrahedronBull Chem Sot JpnSynthesisJACSSynth CommunJCS, Chem CommChem LettSynLettJ. Org. Chem.Tetr. Lett.Citationsxx INTRODUCTIONCompendium of Organic Synthetic MethodsCompendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)CHAPTERPREPARATIONSECTIONOF ALKYNES1: ALKYNESFROMALKYNESMe2CHCH21,THF——–SiMePhzt ;SiMePh,SmIzSm80% Murakami.M,; Hayashi, M.; Ito. YJynlett,1994,179 Ph(CH2)40ACPhPh , toluene5% MO(C0)6 , llO°C , 2o”c 4-chlorophenolAcO(H2C)4Kaneta, N.; Hikichi,AcO(H2C)4K.; Asaka, S.; Uemura, M.; Mori, M. Chem. L&t., 1995,80% 1055REVIEW: “Palladium And/Or Copper-Mediated Cross-Coupling Reactions Between 1-Alkynes And Vinyl, Aryl, 1-Alkynyl, 1,2Propadienyl, Propargyl And Allylic Halides Or Related Compounds. A Review,” Rossi. R,; Carpita, A.; Bellina, F. Org. Prep. Proceed. Znt., 1995, 27, 129SECTION2: ALKYNESFROMA4CID DERIVATIVESNO ADDITIONALSECTION3: ALKYNESFROMALCOHOLSNO ADDITIONALSECTION4: ALKYNESFROMEXAMPLESAND THIOLSEXAMPLESALDEHYDESNO ADDITIONALEXAMPLESCompendiumSECTION5:of Organic Synthetic Methods, Vol9ALKYNES FROM AND ARYLSALKYLS,NO ADDITIONALSECTION6:ALKYNESFROM7:ALKYNESAMIDESFROMEXAMPLESAMINESNO ADDITIONALSECTION8:ALKYNESFROMEXAMPLESESTERSNO ADDITIONALSECTION9:ALKYNES FROM THIOETHERSEXAMPLESETHERS,NO ADDITIONALSECTION10:ALKYNESMETHYLENESEXAMPLESNO ADDITIONALSECTIONFROMEPOXIDESHALIDESAND SULFONATESHO.++K2C03N.D.P, Synlett, 1995,ANDEXAMPLES-NO2Pd/C , PPh3, CuI , DMEBleicher, L.; Cosfwd.Section 1098% 111 5Bu [email protected] R.W.; Gabel, C.J.; Ji, J. TetrahedronLett., 1994, 35, 6993Section 15SECTIONAlkynes from Misc.11:ALKYNESFROMHYDRIDESFor examples of the reaction RC=CH + R&C-C=CR1, (Alkyne-Alkyne). NO ADDITIONALSECTION12:ALKYNESFROMPh ITaniguchi,KETONESY.; Takai, K.; Fujiwara,TMSC(Li)Nz,THF-78OC + reflux Me Miwa, K.; Aoyama. T.: Shioiri, T, Synlett, 1994,13:ALKYNESFROM14:PhPhALKYNESFROM67% Y. Chem. Lett., 199% 1165P-Me58%107NITRILESNO ADDITIONALSECTION-1OOC ,20 minSiMe3Y.; Fujii, N.; Makioka,SECTIONEXAMPLF;Yb,THF,HMPAsee section 300EXAMPLESALKENES OSiPhzt-BuNaHMDS , THF -100°C Grandjean, D.; Pale, P.; Chuche, J. TetrahedronSECTION15:ALKYNESFROM98%L&t., 1994, 35, 3529MISCELLANEOUSCOMPOUNDSFVP (750°C) w t-BuAitken. From A&ken. 1994,=t-Bu82% R,A,; Atherton, J.I. J. Chem. Sot., Per-kin Trans. l., 1994, 128 1 arylC0 derivatives: R.A.; Horsburgh, C.E.R.; McCreadie, J.G.; Seth, S. J. Chem. Sot., Perkin Trans. l., 1727SECTIONCompendium15A:of Organic Synthetic Methods, Vo19PROTECTIONOF ALKYNESNO ADDITIONALEXAMPLBSection 15ACompendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)Section 17Acids from AcidsCHAPTERPREPARATIONSECTION16:SECTIONOFACIDACID DERIVATIVESACID17:DERIVATIVESFROMNO ADDITIONALEXAMPLESDERIVATIVESFROMALKYNESACIDDERIVATIVESC02H HOHaG,, @b, A BuLi, THF-HMPAA IOTsJvOMe Me0Me0Kusumoto.T.;1) 82% (10 Ichikawa, S.; Asaka, K.; Sato, K.; Hiyama, T. Tekhedron Lett., 1995,36,0 C02HKF , microwave,4 min 0OAcC02H95%ee]Mikami. K,; Yajima, T.; Terada,M.; Uchimaru, T. Tetrahedron Mt., 1993, 34, 7591 mSnBu3, MS4A, CH2C12 t 20% (binol)TiClz , rt , 2dPhCHO96% (82% ee , S) Costa, A.L.; Piazza, M.G.; Tanliavini, E,; Trombini, C.; 1[Jmani-Ronchi. A, J. Am. Chem. Sot., 1993, 115, 7001 1.Ti(OiPr)dl,l’-bi-2-naphthol , MS4A CH2C12,refluxPhCHO-78OC,10 min 2. mOH PhkSnBu3 , -20°C, 70h88% (95% ee, R) J(eck. G&; Tarbet, K.H.; Geraci, L.S. J. Am. Chem. Sot., 1993, I15, 8467 1. Et$Zn ,25OC, 10% Lie\\ PhCHO 2.2N HCl 80% ee Mehler, T.; Martens.;Wallbaum, S. Synth. Commun., 1993, 23, 269 11. ZnEt2 , 10%CPPhCHON H11”1CPh20HOH2.2N HCl , -2OOC 100%ee Wallbaum, S.; m. J, Tetrahedron Asymmetry, 1993, 4, 637 With a chiral oxazoline additive, 60% ee J.m Tetrahedron Asymmetry, 1993, 4, 649 Allen, J.V.; Frost, C.G.; W-s.16Compendiumof Organic Synthetic Methods, Vol9Section34B1. BuLi 2. PhCHOCPhzOHOHN Me3. znEt24.2N HClBehnen, W.; Mehler, T.; Martens. TI Tetrahedron Asymmetry, 1993,4, 1413OHEt2Zn , toluene , hexanePhCHO98% ee , SA 95% (85% ee, R)Etde Vries, E.F.J.; mee. 1987FitJ,; Kruse, C.G.; van der Gen, A. Tetrahedron Asymmetry, 1993, 4, OHZnEt2,5% iPr2NHPhCHOy i5%PhLPh-quant. (46% ee , R) ShengJian, L.; Yaozhonrr. J,; Aiqiao, M.; Guishu, Y. J. Chem. Sot., Perkin Trans. I., 1993, 885 Et2Zn . PhMe , rt PhCHO90% (96% ee , R) ao.Rx;Kim, N. Tetrahedron Lett., 1994, 35, 4115 CHo IMe2Zn , PhMe , O°C, NHTfTi(Ot-Bu)4,8% TTPWINHTfwith Ti(OiPr)d – 80% yield, 0% ee Nowotng, S.; Vettel, S.; Mel, P, Tetrahedron Lett., 1994, 35, 453917Alcohols from AmidesSection 36Bu$n PhCHO , (R)-Binol +0.5 Ti(OiPr), , -2O”d /..(141) 48%>99% ee Keck. G.E,; Krishnamurthy, D.; Chen, X. Tetrahedron Lett., 1994, 35, 8323 PhCHOOHZnEtz , hexaneftoluene, 10% chiral ligand 20°C, 28h72% (80% ee) Perez-Encabo,A. Tetrahedron Asymmetry, 1994, 5,And&, KM.; Martinez, M.A.; Pedro-; 67ZnEt;! ,5% chiral ligand PhCHO16h 70% (68% ee , R)Ishizaki, M.; Fujita, K.; Shimamoto,M.; -0.0, Tetrahedron Asymmetry, 1994, 5, 411Et$ZnPhCHOMe%4 * N 3P h‘\cPh-LSH94% (100% ee)Kanrz, J,; Lee, J.W.; Kim, J.I. J. Chem. Sot. Chem. Commun., 1994, 2009CHOP ’PhWatanabe,M.; Soai.OHEt$n ,18hPh J. Chem. Sot., Perkin Trans. I., 1994, 3125quant. (93% ee)18Compendiumof Organic Synthetic Methods, Vol9Et$Zn ,22OCPhCHO 10% Stingl, K.; w.~111 CH (Mes)OLi00Section34B) *PhL 70-90% (86% ee , S)N BnJ, Liebigs Ann. Chem., 1994,49 1 Et$n , chiral ferrocenecatalystPhCHO85% (55% ee , R)toluene mawa.S,; Tsudzuki, IS. Tetrahedron Asymmetry, 1995, 6, 1039PhCHO CH2C12, -78OCPhw 93% (79% ee)I(obavashl.. S,; Nishio, K. Tetrahedron L&t., 1995, 36, 6729 Bu3Sn-, CH2C12,MS * c7H15L 58% (87% ee) 20% Zr-BINOL derivative Bedeschi,P.; Casolari, S.; Costa,A.L.; Tagliavini, E,; Umani-Ronchi, A. Tetrahedron Lett., 1995, 36, 7897 C7H&HO1. chiral Ti complex , ether Ph/CHO *2TFA,THFpi0OTMS 97% (80% ee) Singer, R.A.; &reira.E.M, J. Am. Chem. Sot., 1995, 117, 12360NON-ASYMMETRIC Sn(CH$H=CH& Ph-ALKYLATIONS, D-arabinose, rtCHO 5% Sc(OTf), , aq. MeCNHachiya, I.; Kobayashi, S. J. Org. Chem., 1993, 58, 6958PhL98%Section 36Alcohols from Amides/mPh19PhCHO , Et$n , THF cat. Pd(PPh& , rt ,3hH IPJJ88% Yasui, K.; Goto, Y.; Yajima, T.; Taniseki, Y.; Fugami, K.; Tanaka, A.; Tamaru. Y, Tetrahedron Lett., 1993, 34, 7619 diethyl ether, -5OOC PhCHO98% t-Bu-Et(99 syn;anti) Wissing, E.; Havennith, R.W.A.; Boersma, J.; Smeets, W.J.J.; Spek, A.L.; van Koten, G,J. Org. Chem., 1993, 58, 4228 BuCHO + t-BuCHgHOPhBu OHPhTi(OiP& , -4OOC 2 MAPH , PhLi , -78OCPht-BuHg +OH 1) 60% 10.8) 60%.. ..(3 3 (1’MAPH = ArOAr, Ar = 2,5diphenylphenyl Maruoka, K.; Saito, S.; Conception, A.B.; Yamamoto. H, J. Am. Chem. Sot., 1993, 115, 1183 , THF/aq. HClC7H fi—CHO20°C, lhC7Hl5L>99% Yanagisawa, A.; Inoue, H.; Morodome, M.; Yamamoto. H, J. Am. Chem. Sot., 1993, 115, 10356 eSnBu3, CH2C12, 25OCPhCHO83%5% Ir(CO)(PPh&C104, 30h Nuss. J.M,; Rennels, R.A. Chem. Lett., 1993, 197 1. e, SnC12.2 Hz0 *PhCHO NaI,DMF,hL2,30%NH4F,H20 89% Imai, T,; Nishida, S. Synthesis, 1993, 39520Compendiumof Organic Synthetic Methods, Vo19Section34B1. Bu$nSiMe3, THF, rt 3h,[email protected] H30+SnBu3Bhatt, R.K.; Ye, J.; Falck. J.R. Tetrahedron Lett., 1994, 35, 4081PhCHOSnBu35% Yb(OTf)3 85% Aspinall, H.C.; Browning, A.F.; Beeves N,; Ravenscroft,P. Tetrahedron Lett., 1994, 35,4639 mBr,DMF,rrt *ph//CHo GeI2 , lhPhi 85%Hashimoto, Y.; Kagoshima, H.; -0.K, Tetrahedron Lett., 1994, 35,4805OTIPS TIPS0Ih40#‘,,, OTIPS /1 [email protected] &HO , Me2AlCl , hexane -78OC,17hSMe chiralitytransferene reactionMasaya, K.; Tanino, K.; Kuwajima. I, Tetrahedron Lett., 1994, 35, 7965BuGn-noMe :.I::b’” *-780zpJOMeOMe90% (70:30 de) Colombo. L,; DiGiacomo, M.; Brusotti, G.; Delougu, G. Tetrahedron Lett., 1994, 35, 2063 H1. Li (powder) , naphthalene PhS02Et 2. Li (powder) , naphthalene * 3. PhCHO Guijarro, D.; m.b& Tetrahedron Lett., 1994, 35, 2965E -(I61% PhSection 36Alcohols from Amides21*3SiMQsink3l.Ga,KI,LiCl PhCHO , TI-IF , reflux w 2. H30+ H 4 Br+ H,8‘PhPh ..(91 Han, Y.; Huansz. Y.-Z, Tetrahedron Lett., 1994, 35,9433C,H7-SnBugcd413cHo9) 95%HOw7BuSnC13, CHCl3 , O°C..(98 Mipki.2) 86%H,; Yamamura, K. Chem. Lett., 1994, 897 10.5 CuCl , THF ) It1. mBrPhCHO 1.5 SnClp2 Hz0 , Id 2.30% aq. NI-IPPhL 98%T.Y; Nishida, S. J. Chem. Sot. Chem. Commun., 1994, 273Ph EtCHO , Zn , aq. NH&I, Ph-ClEtOH 98% (73:27) Rairama, R.; Ahonen, M. J. Chem. Sot. Chem. Commun., 1994, 1217WR.; lTHF *. .cat. Pd(PPh& , PhCHO wso2phEt+,THF , refluxPh 86%Clayden, J.; lulia.M,J. Chem. Sot. Chem. Commun., 1994, 190522Compendiumof Organic Synthetic Methods, Vol9mso2phl*Section 34Bpd(pph3)42.2 Et2Zn , CgHlgCHO THF , reflux Clayden. JJ Julia, M. J. Chem. Sot. Chem. Commun., 1994,226l Ph PhCHzSiMe3, hv , MeCNOSiMe3Mg(C104)2, 6.5hFukuzumi. S,; Okamoto, T.; Otera. J, J. Am. Chem. Sot., 1994, 116, 5503 Cl 2: PhCHO ,THF , -78OC ’ Ba* c7Hyph+ C7H15HO47HfiPh ..3) 80% (>99:1 E.-z) Yanagisawa, A.; Habaue, S.; Yasue, K.; mamoto. K J. Am. Chem. Sot., 1994, 116, 6130(97CHOQH = MSnBu3> InC13, acetone, Sh , -78OC+ rt (98:2 anti:syn)Mar&B.J.k; Hinkle, K.W. J. Org. Chem., 1995, 60, 1920 1. PhCHO , DMF , O°CmSiQ32. H20 Kobavashi. S,; Nishio, K. J. Org. Chem., 1995, 60, 6620PhSection 36Alcohols from [email protected]$rCpCi ,20% ZnBr2 * THF ,3h, 25OCPhCHO Zheng, B.; Bebnik.23Hz088%J. Org. Chem., 1995, 60, 3278 In, H20,30 minPhCHOBr&::OH PhBr75%I& C-J, Tetrahedron Lett., 1995, 36, 517Me 1. Ti(OiPr)4 , iPrMgC1OHHOi Ph . 84) 81% (16 Harada,K.; Urabe, H.; Sate. FcTetrahedron Lett., 1995, 36, i203 Nakagawa,T.; Kasatkin, A.; Sate. F, Tetrahedron Lett., 1995, 36, 3207~cHooo1. TMSOTf, CH& MqS , -78°C–2. Bu$nCH2CH=CH2 -40°C 3. TBAFd3 (>99m.OH’ 91% MPMO Kanq. S.-K,; Park, D.-C.; Park, C.-H.; Jang, S.-B. Synth. Commun., 1995, 25, 1359Alcohols from AmidesSection 36BrNPhCHO25, Sn , Me$iCl 89%Bu&Br , MeOH, rt ,4h Zhou, J.-Y.; Yao, X.-B.; Chen, Z.-G.; Wu. S.-H,Synth. Commun., 1995, 25, 3081PhCHOaSnBu3 ,THF,lt,4d * PhL90%pta2(pph3)2Nakamura, H.; Asao, N.; mote.Y, .I. Chem. Sot. Chem. Commun., 1995, 127313CHOCH2C12-H20 (9.1 .. . H20, Bu$JBr (1 asuama. Y,; Kishida, M.; Kurusu, Y. J. Chem. Sot. Chem. Cohun.,9) 48% 99) 48%1995, 1405REVIEW: “Synthetic Organoindium Chemistry: What Makes Indium So Appealing,” Cintas. P, Synlett, 1995, 1087ALCOHOLS AND THIOLS FROM ALKYLS, METHYLENES AND ARYLSSECTION 35:No examplesof the reaction RR1 + ROH (R1 = alkyl, aryl, etc.) occur in the literature. For reactionsof the type RH + ROH (R = alkyl or aryl) seeSection 41 (Alcohols and Phenolsfrom Hydrides). NO ADDITIONAL EXAMPLESSECTION 36: ALCOHOLS AND THIOLS FROM AMIDES 0 C6h3LiBH3P-Pyr , THF, 25OC LAN Pyr = pyrrolidino 3Fisher, G.B.; Fuller, J.C.; Harrison, J.; Goralski, C.T.; Sinearam. B, Tetrahedron Lett., 1993, 34, 1091(-13/OH71%26Compendiumof Organic Synthetic Methods, Vol9Section 39SECTION 37: ALCOHOLS AND THIOLS FROM AMINES NO ADDITIONAL EXAMPLESSECTION 38: ALCOHOLS AND THIOLS FROM ESTERS Pi,180°C, 15he H+Bu 68% OBu Vega, F.R.; Clement, J.-C.; des Abbayes,H. Tetrahedron Lett., 1993, 34, 8117 Mg , MeOH, rt ,2.5h Me0 Y.-C,; Lebeau,E.; Walker, C. Tetrahedron Lett., 1994, 35, 620798%1. PMHS , Ti(OiPr)J , THF Ph-C&Me2. NaOHPhCH20H86$PMHS = polymethylhydrosiloxane Breedon, S.W.; bwrence. N.J, Synlett, 1994, 833 1.2.5 eq. PHMS ,25% Ti(OiPr)d 65OC, Id CgHlg-COzEt t 2. aq. NaOH , THF Reding, M.T.; Buchwald. S.L,J. Org. Chem., 1995, 60, 7884 C7HfiCH2SAcOH C9H1993%BER , Pd(OAc)z , MeOH, reflux w C7HfiCH2SI-IBER = borohydride exchangeresin Choi, J.; Yoon. N.M,Synth. Commun., 1995, 25, 2655SECTION 39:98%ALCOHOLS AND THIOLS FROM ETHERS, EPOXIDES AND THIOETHERS Bu,CuCNLi2,THF OHproducts are converted to alkenes via Swem oxidation and elimination(95Chauret, DC.; Bong, J.hl, Tetrahedron Lett., 1993, 34, 3695+ :Bu 5) 8040%Section 39Alcohols from Ethers27OHOHYJAl(Hg) , 10% aq. NaHC03yield is 23% without ultrasoundalso used Zn rather than Al(Hg)ando Moreno. M.J.S SacMelo, M.L.; CamposNeves, A.S. hedron Lett., 1993:‘34, 353 Salvador, J.A.R.; S&eMelo. M.L,; CamposNeves, A.S. Tetrahedron Mt., 1993, 34, 361 lPhi , Pd(PPh&$, Zn , ZnCl2PhTHF,60°C,4h,NEt3 Duan, J.-P.; Chew. C-H, Tetrahedron Lett., 1993, 34,4019 1. LiI , MeCN , Amberlyst 15 rt, 30min MOTS***+o = 3= = &H2. Bu$nH , AIBN , 80°C toluene ,2hMOT,Federici, C.; &i&i. G,; Rossi, L.; B Lett., 1994, 35, 79799~88%C,; Chiummiento, L.; Funicello, M. TetrahedronH2, Pd-C ,16hP-OH HO86%MeBach, T, Tetrahedron Lett., 1994, 35, 1855l aIOH ’ 10% Pd(OAc)z5 eq. NaO$H ,2 eq. BufiCl 3 eq. iPr2NEt , 80°C, Id N,N-dimethylacetamide Larock. RC,; Ding, S. J. Org. Chem., 1993, 58, 804I (69:31 E.2)70%28Compendiumof Organic Synthetic Methods, Vol9zH *aaSection 39Mg , MeOH,,,[email protected] / BnO7-LC02Me98%p;als. CA; Lee, E.; Lee, G.H. J. Org. Chem., 1993, 58, 1523Pd/C , HCO2NH4, EtOH0 w-h7OH /Al23OC, 2dW-hDragovich. P.S,; Prins, T.J.; Zhou, R. J. Org. Chem., 1995, 60, 492281%98% Beugelmans, R.; Bourdet, S.; Bigot, A.; Zhu. L Tetrahedron Lett., I994, 35, 4349Te9LiBT3,nTsO Kumar, A.; m.D.C: Tetrahedron Let?., 1994, 35, 5583 L-Selectride , THF ,67OC, 12hWheless, K. Tetrahedron Let?., 1994, 35, 87271. TMSN3 , W(Nt-Bu)2(NHIt-Bu)2 ,5d wPh2. H+OH95%[ with Cr(Nt-Bu)2C12;12h – 95% ] Leunn. W.-H; Chow, E.K.F.; Wu, M.-C.; Kum, P.W.Y.; Yeunrr. L.-L, Tetrahedron Let?., 1995, 36, 10729Alcohols Tom HalidesSection 40Ph5% SmI2(THF)z, CH2C12NEt2Et2NH,rt,18h(100OH..0)63%regioselectivity of addition reversedwith Me&N3 to form azide-OTMS Van de Weghe, P.; collin. Tetrahedron Lett., 1995, 36, 1649TMSN3, Ph&bOH, PhH reflux ,2h67% 19% .. Funwara. M.; Tanaka,M.; Baba, A.; Ando, H.; Souma,Y. Tetrahedron Lett., 1995, 36, 4849 l.e-,Ni(II),Mganode,DMF,rt mOPhPhOH2. Hz0 99%Olivero, S.; Dufiach. E, J. Chem. Sot. Chem. Commun., 1995,2497 Additional examplesof ethercleavagesmay be found in Section45A (Protection of Alcohols and Thiols).SECTION 40:ALCOHOLS AND THIOLS FROM HALIDES AND SULFONATES02N-(-)-Br :::v::02N-(-)aBieniarz. C,; Cornwall, M.J. Tetrahedron Lett., 1993, 34, 939a.BrsiMe31. Li dispersion, ether reflux 2. PhCHO , -1OOC lhalso works with ketones M; Hatano,K.; Kimura, M.; Watanabe,T.; Oriyama, T.; Koga, G. Tetrahedron Lett.,1994, 35, 57930Compendiumof Organic Synthetic Methods, Vol9Section421. Me3ZnLi , THF , -78OCPh-I2. Me3Al, CHg12, O°C, lhPh 55%Kondo, Y.; Takazawa,N.; Yamazaki, C.; Sakamoto.,J. org. chem., 1994, 59,4717PhCHO -PhCHCl2 2. NaB0~4 [email protected] ,2h1. Bug , t-BuLi , -78OCPC15PhJLG.W.; Lin, N.-S.; Yu, S. Tetrahedron Let?., 1995, 36;8545Bu 64%NHBnNHBn0 Yang, R.-Y.; Dai. I..-& Synth. Commun., 1994, 24, 2229G Br1. HC02NHEt3CO2H 2.H2080% J,; Renyer, M.L.; Veerapanane,H. Synth. Commun., 1995, 25, 3875Mer.SECTION 41: ALCOHOLS AND THIOLS FROM HYDRIDES0 /1. e- , CF$02H, CH2C12,NEt32.H20(t /Fujimoto, K.; Maekawa, H.; Tokuda, Y.; Matsubara,Y.; Mizuno, T.; Nishiguchi.OH 73% SYnlett,1995,661SECTION 42: ALCOHOLS AND THIOLS FROM KETONES The following reaction typesare included in this section: A. Reductionsof Ketonesto Alcohols B. Alkylations of Ketones,forming Alcohols Coupling of ketonesto give diols is found in Section 323 (Alcohol + Alcohol).Section42AReductionof Ketones31SECTION 42A: REDUCTION OF KETONES TO ALCOHOLS ASYMMETRICREDUCTION OH = Z IBH3, THF , 80°C w> 90% (92% e-e,R)P iiQuallich. GJ,; Woodall, T.M. Tetrahedron Lett., 1993, 34,4145Me85% (76%ee,R)2.1N HC1 P Me Balm. (3,; Elder, M. Tetrahedron Lett., 1993, 34, 6041 G. candidiumCQzEt NC02Et cyclopentanol H20, 70h(7193syn:anti)Me QH E _=immobilized G. candidium hexane ,3h cyclopentanol-/I/(955 syn:anti)G. candidium = Geotrichum candidumNakmura. KJ Takano, S.; Ohno, A. Tetrahedron Lett., 1993, 34, 6087 0.6 BHpSMe2 , THF rt,clh Me10%PAH *Y HOH = =PhlP&MeMeP ’ ‘Ph82% (27%ee,S)Bums, B.;,Studley, J.R.; Wills. M, Tetrahedron Lett., 1993, 34, 71051.ld4j~; PMe$iCl Me2.2N HClH *C02Et = = = = IPhLMe92% (84% ee, R)&-&IL C,; Seger,A.; Felder, M. Tetrahedron Lett., 1993, 34, 807932Compendium of Organic Synthetic Methods, Vo19Section 42A2. SmI3, THF , ICHgH21 3. quench quant. (97% ee , R) Evans. D.pL; Nelson, S.G.; Gag&, M.R.; Muci, A.R. J. Am. Chem. Sue., 1993, 115, 9800 OH1. P-TADDOL complex , Ph2SiH2 , PhH50% (29.5:70.5 R.-S)r~mw112 2. TsOH , MeOH-APhTADDOL = a,a,a’,&tetraaryl-4,5-dimethoxy-1,3-dioxolane Jakaki, J.-i.; Schweizer, W.B.; Seebach. D, Helv. Chim. Acta, 1993, 76, 2654 Bakers yeast (cell free extract) OAcIshihara, K.; Sakai, T.; Tsuboi, S.; IJtaka, 0OAcNaDPH ,8h62% (>99% ee, S) Tetrahedron Let?., 1994, 35,4569[ (COD)Rh(DiPFc) 1’ OTf HPh A60 psi H2 ,25OC ,4hL PhOHDiPFc = 1, l’-bis-(diisopropylphosphino)ferrocene quant. Burk. MJ,; Harper, T.G.P.; Lee, J.R.; KaIberg, C. Tetrahedron Let?., 1994, 35, [email protected];;dcy%@l.7%e,sJHong, Y.; &D. Y.; Nie, X.; Zepp, C.M. Tetrahedron Let?., 1994, 35, 6631 Ph1. Ph$iH2 ,5% Rh-diferrocenylTHF , o”c dichalcoginidePh *67% (50% ee , R) 2.0.5M HCI/MeOH 0 OH Nishibayashi, Y.; Singh, J.D.; Segawa, IS.; Kukuzawa, S.i.; Uemura, S, J. Chem. Sot. Chem. Commun., 1994,1375Section 42AReduction of KetonesBakers yeast sugarOHSHC02EtCO2EtC02Et.. (77 55% ee Tetrahedron Asymmetry, 1994, 5, 403Nielsen, J.K.; Madsen.Me33/L23immobilized Geotrichum candidurni)H = =w hexane 2-hexanolPhMeAPh73% (>99% ee , S) Nakamura. K,; Inoue, Y.; Ohno, A. Tetrahedron Lett., 1995, 36, 265 OHOH PhOH(-)-B -chlorodiisopinocampheylborane -15OC + OOC, THF, pyridinePh99% (96.4% ee) . Shteh. W.-C,; Cantrell Jr., W.R.; Carlson, J.A. Tetrahedron Lett., 1995, 36, 3797 Hz, (S-BINAP)zRuBrz COzMe* MeOH, rt ,48hOH == =C02Me80% (97% ee)Genet.; Ratovelomanana-Vidal, V.; Ctio de Andrade, M.C.; Pfister, X.; Guerreiro, P.; Lenoir, J.Y. Tetrahedron Lett., 1995, 36, 4801iLH2 , iPrOH , chiral bis-phosphine>99% (87% ee, R) * PhL chiral bis-amine Ph Ohkuma, T.; Ooka, H.; Hashiguchi, S.; Ikariya, T.; Novori. R,, J. Am. Chem. Sot., 1995, 117, 2675Ph[RuC12(mesitylene)]2, KOH , 15h TolO$HN+/-fPhNH2PhHashiguchi, S .; Fujii, A.; Takehara, J.; Ikariya, T.; &yori. 7562OH PhA 95% (97% ee, S) & J. Am. Chem. Sot., 1995, I1 7,34Section 42ACompendium of Organic Synthetic Methods, VoI 91. Ph2SiH2 , THF , 1% RhCl(NBD)zL chiral ferrocenyl phosphine ligandOH 90% (87% ee , S)PhA 2. H30+ * PhA . Havashl. T,; Hayashi, C.; Uozumi, Y. Tetrahedron Asymmetry, 1995,6, 2503 1.0.1 chiraI diol , hexane , -3OC , catecholborane 2. H30+ quant. (82% ee) Giffels, G.; Dreisbach, C.; Kragl, U.; Weigerding, M.; WaIdmann, H.; Wa~&ey. C1,Angew. Chem. Int. Ed. Engl., 1995, 34, 2005NaBH4, EtOH Co (P-oxoaldiminato) complex99% (73% ee , S) Nagata, T.; Yorozu, K.; Yamada, T.; Mukaiyama. T,Angew. Chem. Int. Ed. En& 1995, 34, 2145NON-ASYMMETRICo= 0REDUCTION1. CdCl$Mg (powder) THF,15minOH92%2, H20Bordoloi. M, Tetrahedron Lett., 1993, 34, 1681t-Bb. olrm(-)LiAIH(zt2cMe3)3t-Buwith LiAlH(OCMe3)3 – 90: 10 trans:cis Cr.; Deberly, A.; Toneva, R. Synlett, 1993, 585(-)OH5:95 trans:cisCu(I1) exchanged cationic resin ‘.,u-(-=’NaBH4, EtOH, O°Ct-Bu-(-)-oH 98%Sarkar. A,; Rao, B.R.; Ram, B. Synth. Commun., 1993, 23, 29135Reduction of KetonesSection 42A& :;:I;;Fuller, J.C.; Staangeland, E.L.; Goralski, C.T.; Sinearam.o=Tetrahedron Lett., 1993, 34, 257iPrOH , SiO2-Zr catalystInada.;92%OHreflux87%Shibagaki, M.; Nakanishi, Y.; Matsushita, H. Chem. Lett., 1993, 1795OMe TiC14, MeflBH4 tPhCH2C12 , -78°CKi other reducing agents also used Sarko, CR.; Guch, I.C.; Dime.t-Budo(99 M, J. Org. Chem., 1994, 59, 705Liz;;;;H7)2t ,:1)93%&OH99% Harrison, J.; Fuller, J.C.; Goralski, CT.; Singaram. B, Tetrahedron Lett., 1994, 35, 5201 OH0 1. Cp2TiC12/NaBHq, 5 min 2.1 N NaOH % Barden, M.C.; Schwartz. J, J. Org. Chem., 1995, 60, 5963B 0(MeO)3SiH , LiOMe , etherPh-20°C, 9h*HOlph (8XPh .92) quant.wth (Me0)$iI-I/HMPA/LiOMe/O°C/2h + (9O:lO) 98% Hojo, M.; Fujii, A.; Murakami, C.; Aihara, H.; Hosomi. Tetrahedron Lett., 1995, 36, 57136Compendium of Organic Synthetic Methods, Vol9Section 42BHz (8 atm) , cat. RuClz(Binap)(dmf), -HiPrOH , diamine , KOH ,28OCd Ph Ph Ohkuma, T.; Ooka, H.; Ikariya, T.; Noyori. R,J. Am. Chem. Sot., 1995, 117, 10417cat. [NiClz(PPh&, cat. NaOHOH 82%- PhA iPrOH , Ar ,3Oh, heat PhA lyer. &; Varghese, J.P. J. Chem. Sot. Chem. Commun., 1995, 465SECTION 42B: ALKYLATIONOF KETONES, FORMING ALCOHOLSAldol reactions are listed in Section 330 (Ketone-Alcohol)o=MeHebri, H.; Duiiach.;e’ , SmC13, DMF , 20°CPerichon, J. Tetrahedron Lett., 1993, 34, 1475 3 eq. Me$=CH2 , THF 0 -1OOC -+ rt91% Hamett, J.J.; Alcaraz, L.; Mioskowski, C.; Martel, J.P.; LeGall, T.; Shin, D.-S.; Falck. J.K Tetrahedron Lett., 1994, 35, 2009C6H13-0.JLe’7 CH3DMF , -OH Bu#BF4.,,,330H OH89% T,; Morishima, Y.; Moriyoshi, N.; Ishifune, M. J. Org. Chem., 1994, 59, 273Section42BAlkylation of Ketones371.2.2 eq. SmI2 , THF 2 eq. t-BuOH2. H30+53% (1:l) &lolander. G.A,; McKie, J.A. J. Org. Chem., 1994, 59, 3186 0.05 CeC13,lh , THF 01.1:= -MgBr93% rtrov. V,; Bratavanov, S.; Simova, S.; Kostova, K. Tetrahedron Lett., 1994, 35, 6713mBr C02Et, In 91Oh CO2Etaq. MeOHBr9 wlust o=76%Ii. C.-k, Lu, Y.-Q. Tetrahedron Lett., 1995, 36, 2721THF , 1Sh1.8 Et$Zn , Ti(OiPr)4 , hexanePhCHO Hang.;80%usescommercialZn dust Majee, A.; Das, A.R. Tetrahedron Lett., 1995, 36,&BRanu.;OH-23°C , 0.1 chiral catalyst Guo, C. Tetrahedron Lett., 1995, 36, 4947PhMe3Ti*MeLi , ether W-h97% 99% ee, S-5OOCEt* W-hselective for conjugated ketones in the presence of non-conjugated ketones M&& I&; Leung, C.W. J. Am. Chem. Sot., 1994, 116, 37178%Compendiumof Organic Synthetic Methods, Vol938Section42B1. 10%CpzTi(PMe3)2,Ph#I-I2 1111111111OH6 >60%Kablaoui, N.M.; Buchwald. S.L,J. Am. Chem. Sot., 1995, 117, 6785e’ , MeCN , ZnBr2 Bu4N BF4(95 Row5) 85%Y,; Derien, S.; DuWach,E.; Gebehenne,C.; Perkho;, J. Tetrahedron, 1993, 49, 7723wBr *Zn , aq. NH&l, THF(54 Ahonen, M.; SiiSholm.m’ PhL..46) 73%Chem. Lett., 1995, 341Ph9PbCr(~eda) THF , -6OOCPh 77%WiDf. P,; Lim, S. J. Chem. Sot. Chem. Commun., 1993, 1655. 11.G,; Marcantoni, E.; Petrini, M. Angew. Chem. Int. Ed. En&70% 1993, 32, 106139Alcohols from AlkenesSection44SECTION 43: ALCOHOLS AND THIOLS FROM NITRILES 1. Li (excess), PhCHO , -3OOC + MeCN 5% 4,4’-his-t-Bu biphenyl 2. H20, HCl Guijarro, D.; Yus. M, Tetrahedron, 1994, 50, 3441H 39%Me-LPhSECTION 44: ALCOHOLS AND THIOLS FROM ALKENES 1. Ti(BH& , 30 min CH2C12,-2OOC -2.10% K2CO3c(,aOH1.2) 82% (1 Kumar, K.S.R.; Baskaran,S.; Chandrasekaran,S. Tetrahedron Lek., 1993, 34, 171 MeZn(BH& , DMF SiO2, rt ,30 min 30) 80%(70 &nu. B.C,; Charkraborty, R.; Saha,M. Tetrahedron Lett., 1993, 34,‘4659l.Mg*,THF,rt 2. ethylene oxide THF , -78OC 3. co2, oc + rtOI-OH 86% with Mg* = 8 Li, naphthalene,4 MgC12, THF, 3 Li H30+ at -78OC Sell, M.S.; Xiong, H.; We. R.D. Tetrahedron Lett., 1993, 34, 6007 6011 40°C 4. H30+ , 0°C + -9o 69%1.2 eq. Ph02BH, THF Nb catalyst, 25OC, Id 2. H202, NaOH Burgess.K,; Jaspars,M. Tetrahedron Lett., 1993, 34, 6813 also with CpzTiC14, see Burgess.K,; van der Donk, W.A. Tetrahedron L&t., 1993, 34,681740Section 44Compendiumof Organic Synthetic Methods, Vo19By 99% ee) 115, 125691993,Hz, rt , lh , MeOWH20 RuC13,TOATOA = trioctylamine Fache, F.; Lehuede, S.; LeMaire. M, Tetrahedron Lett., Ph 0 Cho, I.S.; Lee, B.; m1995,36,99% (ciskans = 1.5) 885[ (t-Bu2PH)Pd(Pt-Bu)2]2, H2 ,02 THF/CH2C12,6hTetrahedron Lett., 1995, 36, 6009aq. Ba(OH), , NiAl(Raney alloy) 54%60°C, lhBr Br Tsukinoki, T.; Kakinami, T.; Iida, Y.; Ueno, M.; Ueno, Y.; Mashimo, T.; Tsuzuki, H.; Tashiro, M. J. Chem.Sot. Chem. Commun., 1995, 209 H2, [ W2(~&t’BU)6(@)2Barry, J.T.; Chisholm.M.H, .I. Chem. Sot. Chem. Comma,1995,no yield 159974Section 74BCompendium of Organic Synthetic Methods, Vo19SECTION74B: Formationof ArylsOMe / LiCl , CuBr , inhibitor Pd(PPh& , dioxane , refluxOMe &.& J.M.; MartoreU,G. J. Org. Chetn.,1993, 58, 1963Crrissom, J.W,; Calkins, T.L.; McMillen,bMeH.A. J. Org. Chem., 1993, 58, 65% 50 at.mCO, [email protected] PdCl2W’bh 9 mt3PhooAcPhH , 140°C, 3h Ishii, Y.; Gao, C.; Xu, W.-X.; Iwasaki,M.; Hidai. MJ.OAc 69% Org. Chem., 1993, 58, 6818HSiMe$-Bu , C) (50 atm) Ru~(CO)~~/PCY~, 140°C,20h*:::: 45%Chatani, N.; Fukumoto, Y.; Ida, T.; Murai.S, J, Am. Chem. SM., 1993, 11.5, 11614PhOH , PhMe ,180”C t7h %Danheiser, R.L,; Gould, A.E.; de la Pradilla, R.F.; Helgason, A.L. J. Org. Chem., 19%55145%Section 74B75Formation of Aryls20% Ni(O)-PPh3 , HC=CH N—Ts THF,23OC, 12h 91% Sato, Y.; Nishimata, T.; Mori. M, .I. Org. Chem.,1994,59, 61331. PhNH2 2. Pd(OAc), , MeCN PhCHO B;-;FHT3/AQtZRamaRao.AV,; Reddy,K.L.; Reddy,M.M. Tetrahedron Lett.,1994,35,5039OH 1.5 I~wipr)30.1SnC14, 0°C 1.5 (MeO)$iMe3s 78% -Si(iPr)3Angle. SR,; Boyce,J.P. TetrahedronLett., 1994,35, 6461t-BuOOCOPh, Cu(OAc), CuBr , PhH , 80°C, 8.5h56% Tavares,F.; Mevers. A.1, Tetrahedron Lett., 1994, 35, 6803 N-OH Bn5% Pd/C, diethyleneglycol 188OC , diethyl ether, 45 minBn 89%I Ar Ar = 4-methoxyphenyl Matsumoto.M.; Tomizuka,J.; Suzuki, M. Synth. Commun.,1994,24,Al144176CompendiumSECTION74C: AlkylationsSection 74Cof Organic Synthetic Methods, Vol9and Arylationsof Alkenes2 BFjmOEt2 25OCMaietich. G,; Zhang, Y.; Feltman, T.L. Tetrahedron L&t., 1993, 34,441 . Maretich. G,; Zhang, Y.; Feltman, T.L.; Duncan Jr., S. Tetrahedron Lett., 1993, 34, 445 Ar/OH Ph Toluene , -45OC , 18h 2. LiEt3BH 3. MeOH 4. NaBH4. Tomloka.;Ar = 2,6-di-t-Bu-4-OMephenyl Shindo, M.; Koga, K. Tetrahedron80%(84% ee)Lett., 1993, 34, 681+3-l”lDMF , BuflCl , ld 10% Pd(OAc)z ,3 iPr2NEt 66:34 E.-Z, 99% 5 HC02Na Ding, S. Tetrahedron Lett., 1993, 34, 979Larock.;w-4Mecat. Pd(OAc);? , [email protected] DMF ,45OC, overnightC02Me WllOH OH &[email protected], TetrahedronL&t., 1993,34,1133NH275%Section 74CAlkylation of Alkenes77Me1. Et&Cl60% 2. BuZnCl , DMF * BuJ==i OH 5% C12Pd(PPh3)2 2 BuLi ,5h Ay, M.; Gulevich, Y.V.; Noda, Y. Tetrahedron Lett., 1993, 34, 1437 OH. . Nenlshl,;SnBu310hZhang, H-C.; Brakta, M.; DavesJr,. G.D, TetrahedronOTfL&t., 1993, 34, 1571, 30°C, 91h 58% 87%ee,RPd(R-BINAP)2, PhH ProtonSponge C)zawa.F,; Kobatake,T.; wi.Pi0T, Tetrahedron Lett., 1993, 34, 2505Q-I 11I, AIBN , To1 52%46h, 85OCSnBu3 Kinnev. W.A, Tetrahedron Lett., 1993, 34, 2715 PhBr , To1,2% Pd(PPh& phm,, Bu$nmNI-12 R.J&; Geng,B.; &Iore;ill. J.JE J. Org. Chem., 1993, 58, 1443 w-h700w-b31. Me2SCHC02EtBu$nB(Wl3122. H202, NaOAcDem. M.-Z,; Li, N.-S.; Huanrr.Y.-Z,J. Org. Chem., 1993, 58, 194960%47%Compendium of Organic Synthetic Methods, Vo19Section 74CBr J&;OMeQabar, M.N. J. Org. Chem., 1993,58, 44731. PdC12 , LiCl , THF o”c + 25OC ] 2. aq. NH4Cl-PhINH22. PhHgCl , O2 60% Larock. R.C%; Ding, S. J. Org. Chem., 1993,E:z)58, 2081PhOTf , Pd(PPh3)4, 85OC(CH2)8co2Me/9-BBN(74:26&PO4 , dioxaneph-58,2201(cH2)&02Me 87%Oh-e, T.; &Graura. N.: Suzuki. A, J. Org. Chem., 1993, Ph1.2 Et$n , 1.5% PdC12(dppf), THF 2. CuCN.2 LiCl 3.Stadmiiller, Sot., 1993,C02EtH.; Lentz, R.; Tucker, C.E.; S tiidemann, T.; Diirner, W.; Knochel. 115, 7027phi3 eq. EtMgBr , Cp$rCl2 THF,rt,6hSuzuki, N.; Kondakov,D.Y.; Takahashi,T, J. Am. Chem. Sot., 1993, 11.5, 8485J. Am. Chem.Section 74CAlkylation of Alkenes79C02Et N2+BFdC02Et, EtOH2% Pd(OAc)z , 60°C, lhSenguPta.;Bhattacharyya, OH71%S. J. Chem. Sot., Perkin Trans. l., 1993, 1943 OH5 eq. MeMgBr 0.05 PdC12(PPh3)297% VW,;Giesen, V.; Fuest, M. Liebigs Ann. Chem., 1993, 629e, , DMF , Et&104 47% Ni(teta)(ClO& Ozaki. S,; Horiguchi,I.; Matsushita, H.; Ohmori, H. TetrahedronLett., 1994, 35, 725 iMeLDA, TMS-Cl C3H06Et Wright. S.W, TetrahedronTHF , -78OCC3HEt93%Lett., 1994, 35, 1841 Phi , Bu4NHS04,aq. MeOH02Me02Me 5% [Pd(OAc)2/2 PPh3] Jeffery. T, TetrahedronA Ph96%Heck reaction in aqueous media Lett., 1994, 35, 3051Phi , SmIz/THF , 15 min DMSO0 Nazareno, M.A.; Rossi. R.A, TetrahedronPh A/ Lett., 1994, 35, 5185Ph47%Compendiumof Organic Synthetic Methods, Vol9Section 74CPh Pd(OAc)2, Bu3P, 3h IS2CO3 , DMF , 80°C +PhiPh +quant. (78 Ono, IS.; Fugami, K.; Tanaka, S.; Tamaru. Y, Tetrahedron Lett., 1994, 0Majetich.OOCNHMe 6) 35, 41330 2 AlEt, 0°C bSPh10hG,; Zhang, Y.; Liu, S. TetrahedronSPh0 Lett., 1994,4 35,488770%,SnBujPd(PPh3)4, THF ,65OC, lh Matthews,D.P.; Waid, P.P.; Sabol. J.S.: McCarthy. J.R, Tetrahedron66% Lett., 1994, 35, 5177TfO OMeSnBu3OMe 70%B.D,; Cardamone, Rbe9 Guzzi, U. Tetrahedron l/ SnBu3 1. 5% Pd2(dba)3 ,20% AsPh3 w 2.5% TFA , CH2C12 = Rink amide resin Deshnande. M.S, TetrahedronLett., 1994, 35, 561389%Section 74C81Alkylation of Alkenes2 eq. MesSiCHzMgClphwseMeb l?h-siMe3 5% NiC12(PPh&, DME reflux , 1.5h Hevesi.L,; Hermans,B.; Allard, C. Tetrahedron Left., 1994, 35, 6729 1.0.3 q3-C3HSPdC1)2 , HSiPh2F 0.6 o’-diphenylphosphinobinaphthol Ph-79%Phderivative20°C , 10h 2. MeLiMe S iPh2Me96% (66%ee,S) Hatanaka. Y,; Goda, K.; Yamashita, F.; Hiyama, T. TetrahedronNC/‘QLeft., 1994, 35, 7981NH 12NH2Mn(OAc), , CuOAc ultrasound ,4h/ Bosman, C.; D’Annibale.47%A.; Resta,S.; Trorrolo.C, Tetrahedron Bufl+Left., 1994, 35, 8049(Ph3SnF2)‘, THFOTfPh Pd(PPh3)4, reflux ,30 min8-81% A.&; Barcina, J.O.; Cerezo, A. de F.; Subramanian, L.R. Synlett, 1994, 104710% ZrC12(qC&),1.5 BuMgClII, 6h Takahashi. T,; Kotora, M.; Kasai, K. J. Chem. Sot. Chem. Commun., 1994, 2693 ,SiUe3 1. BuLi , THF , -7OOC 2.ZnBr2, -7OOC + 2o”c 3. H30+81%82Section 74CCompendium of Organic Synthetic Methods, Vol9C$-I&Me#H, Et3SiHAcH$(H$)4/SW3tridecane , di-t-Bu hyponitrite 65% Dang, H.-S.; Roberts,.P,TetrahedronLett., 1995, 36, 2875PhSnCl3, aq. KOH ,3% PdC12 *Br*COOHPh*COOH 83%Rai, R.; Aubrecht, K.B.; Collum. D.B. TetrahedronLett., 1995, 36, 3169cylization-Diels-AlderJoumet, M.; B.m J. Org. Chem., 1995, 60, 6885Chavan. S.P,; Ethiraj, KS. TetrahedronLett., 1995, 36, 2281OMeOMe BF3eOEt2, C&I 12, refky 2h56% Maietich.G,; Liu, S.; Siesel, D. TetrahedronLett., 1995, 36, 4749Alkylationsection 74C83of AlkenesPh 10% Pd(OAc)z ,20% Bu3P Phi , DMF, 100°C, 1ShS.-K,; Jung, K.-Y.; Park, C.-H.; Namkoong, E.-Y.; Kim, T.-H. TetrahedronZhang, W.; Dowd. P, TetrahedronLett., 1995,Lett., 1995, 36, 853995% Yu, J.; Cho, H.S.; Falck.TetrahedronLett., 1995, 36, 8577. JEt3, PhMe , reflux5% RuH2(CO)(PPh& 94% Trost.;Ixni, K.; Davies, I.W. J. Am. Chem. Sot., 1995, 117, 5371 1. Me3Al,8%y”Cl$ZrCpz , DCE ,22OC2.02 92% (74% ee)Kondakov,D.Y.; Negishi.J.Am. Chem. Sot., 1995, 117, 10771Compendium of OrganicSyntheticMethods,Vol984OTfDraper,T.L.; mv.Section74DCO,Et,5% PdC12(PPh3)2 w 3 LiCl , DMF , 110°CT&SynZett, 1995, 157 Si(OEt)gSi(OEth, toluene,135OCRu(H)2(CO)(PPh&7 2d50% Kakiuchi, F.; Tanaka,Y.; Sato,T.; Chatani,N.; Murai. S, Chem. Lett., 1995,6791. BC13, CH2C12,O°C PhwPh 2. catechol, PhH 3. PhBr, Pd(PPh& , NaOH Farinola,G.M.; Fiandanese, V.; Mazzone,L.; Naso.F, J. Chem. Sot. Chem. Commun., ph-sMe386% 1995,2523 REVIEW:“RecentDevelopments andNew Perspectives In The HeckReaction,”Cabri.W,; Candiani,T. Accts. Chem. Res., 1995,SECTION74D:28, 2Conjugate Reduction of a&Unsaturated Carbonyl Compounds and Nitriles2% [Pd(Pt-Bu)(PHt-Bu& 02 9 H2(10 psi) I 4Me90%THFJ3h glassautoclave )Sommovigo,M.; u.H.TetrahedronLett., 1993,Me34, 59OH Eta-9 ~&oh6ph//co2phCO (1 atm), [email protected],3O”C 80%bh. x; Fujiwara,IS.; Takahashi,S. Bull. Chem. Sot. Jpn., 1993, 66, 978Section 74D85Conjugate ReductionPhSiH3, 20°C, 16h MOcomplex..(62 Schmidt.T, Tetrahedron38) 95%conversionLett., 1994, 35, 3513NaHTe, EtOH Ph*CHOphmCHOrt ,5h>98%Yamashita.M,; Tanaka,Y.; Arita, A.; Nishida,M. J. org. Chem., 1994, 59, 350 TFA-Et3SiH,30 min -78°C + O°Czhao, Y.; m.variousprotonicandLewisacidsused P,; Keo, E.A. Tetrahedron Lett., 1994, 35, 4179NH4+HC02-, Pd-C25OC,4hRanu.B.C; Sarkar,A. TetrahedronLett., 1994, 35, 8649Bakersyeast, 31°C =, pheNo2 phmNo2 3d . shl&, M..; Yoshida,S.; Kohno,Y. Heterocycles, 1994,37, 55343%limonene, 10%Pd/C, reflux 0o= von Holleben.M.L,; Zucolotto,M.; Zini, C.A.; Oliveira, E.R. Tetrahedron,quant.o=6994, 50, 973Compendium of Organic Synthetic Methods, Vol986Na&Od, aq. dioxane,5O”CPhA, lh *ECHOSection 74EPhiICI-IO selectivereductionof conjugatedDhillon. RS,; Singh, R.P.; Kaur, D. Tetrahedroncarbonyl C=C units L&t., 1995, 36, 1107Sm, 12, MeOH , 1min t Bessho,K.; Yanada,K. Synlett,a;C02Meph//C02Et97% 1995,443C02MeBER-CuS04, MeOH, rtBER = borohydrideexchangeresin Sim, T.B.; Yoon. N.M,SynZett,1995,94%726NaBHeBiC13,95%EtOH twC02Et Ren,P.-D.; Pan,S.-F.; Dong, T.-W.; Wu. S.-HJynth.CO2Et 98%Commun., 1995, 25, 3395Bakersyeast,; Saitou,K.; Hida,K.; Ohno,A. TetrahedronSECTIONAsymmetry, 1995, 6, 214374E: Conjugate AlkylationsRanu. B.c; Saha,M.; Bhar, S. TetrahedronL&t., 1993, 34, 1989Section 74EConjugate AlkylationsPhS-0’ Li+EL CH2C12 2d, -78OC 6‘t,CO2Me87C02MeSPh + 2(15 Corey. E.J,; Houpis, I.N. TetrahedronLett., 1993, 34, 24kP 1. PhMgBr , CuBr*SMezh Tv2.NBS,THF,-78°CLi, G.; Jarosinski,M.A.; J-In&y. V.J, Tetrahedron Lett., 1993, 34, 2565 0PhguLi , THF , -78OC + TMSCl + TMSCN ; James,B. Tetrahedron81% 83%-kPhLett., 1993, 34, 66893 eq.mSnBu3 0.05(Bu$n)z 6 eq.PhSCH(OMe)z 0.3 M PhH, hv (sunlamp)ea20%Me69%OMe(8: 1 transxis)mk. G&; Kordik, C.P. Tetrahedron Lett., 1993, 34, 6875Me(Boc)NCHzSnBu$s-BuLi TMEDA , CuCN, TI-IFer. m;Alexander,C.W. Synlett, 1993, 40798% NMeBocSection 74ECompendium of Organic Synthetic Methods, Vo1988EtEt 9 Eu( tfc)3 MS , Ccl,, -33OC, 72h-*71% (25%ee)Eu(tfc)3 = [tris-(3-trifluoromethylhydroxymethylene)-d-camphorato] europium (III) Tetrahedron L&t., 1993, 34, 7649 Bonadies, F.; Lattanzi, A.; Orelli, L.R.; Resci, S.; Screttri.1. BnOCH~CH+CH/Cp$Zr(H)Cl 2. MeLi , Me$u(CN)Liz81% rnshutz.R.H; Wood, M.R. J. Am. Chem. Sot., 1993, 115, 12625 0 -31. Ni(aca& 2. -w80% Eshelby,J.J.; Crowley, P.J.; Parsons.P.J,Synlett, 1993, 279 1. Me2CuLieLiIBu/-co2Et2. MeOTf Amdt, S.; Handke,G.; Krause.N, Chem. Ber., 1993, 126,251SO2Ph -1. t-BuBr , Cr(en)2+2 , DMF ,4h * 2.H20t-Bu 78% en = ethylenediamine Tashtoush,H.I.; hstmann. R, Chem. Ber., 1993, 126, 1759S02PhSection 74EConjugate AIkylations89Ph$b , cat. Pd(OAc);! 0AgOAc , AcOH ,25OCCho, C.S.; Tanabe, K.; Uemura.TetrahedronPhLett., 1994,127535,41%3 eq. SmI2,THF ,-78°CTrivellas,A. Tetrahedron Lett., 1994, 35, 1627-E.J.;cat. Pd(OAc)z, NaOAc , Id cat. SbC13,AcOH ,25OC *‘“(‘rf88%Ph Cho, C.S.; Motofusa, S.; IJemura.S, Tetrahedron Lett., 1994, 35, 1739 rMe023 eq.Me$iSnBu3,2 eq.CsF DMF,rt, lh Br Sate,H.; Isono,N.; Okamura,K.; Date,T.; Mori. M, TetrahedronLett., 1994, 35, 2035MeTi(OiPr)dMgCl , TI-IF Ni(acac)z, -15OC + rtBs.; 607585%Kabbara,J.; Nickisch,K.; Neh, H.; Westermann, J. Tetrahedron Mt., 1994, 35,90Compendium of Organic Synthetic Methods, Vo19Section 74Et-BuHgCl , Et3SiH , DMSO ==c) dark, hv (sunlamp) -35OC , llh Russell. G.A,; Shi, B.Z. Tetrahedron Lett., 1994, 35, 3841 C02EtEt$iC02Et 93%iPrCH0, LiNO3, aq.MeCN e’ C02Me +QL 2 34% UT.; Soejima,T.; Takigawa,K.; Yamaguchi,Y.; Maekawa,H.; I(ashimura. S, Tetrahedron Lett., 1994, 35, 4161 YC02teBu 1. BuLi, m -100°C + 3o”c,C02t-B :: = t =2. H-2070% +otherisomersCookeJr.. M.P,; Gopal,D. TetrahedronLett., 1994, 35, 2837PhCHO, Ph2C0 hvKraus.G.A,; Liu, P. Tetrahedron69%Lett., 1994, 35, 7723MeMgCl , CeC13,THFBli.G,; Bosco,M.; Sambri,L.; Marcantoni,E. Tetrahedron Lett., 1994, 35, 8651Conjugate AlkylationsSection 74Ewey.a, Hajra, S.; Ghorai, M.K. Tetrahedron91Lett., 1994,35, 7837MeO&Bu$nHCOzMe(1 Miura,Iondo, T.; Hosomi. A, Tetrahedron, PhHBuC=CH , PhC=CSnEtjWlW-I111) 54%Le ‘tt., 1;94,35,9605, Me&ClNi(acac)z , Dibal , THF , rt ,2h%A80% (>95:5 E.-Z) Ikeda, S.; &to.Y, J. Am. Chem. Sot., 1994,116,5975 CHO94% (93:7 1,4: 1,2) Kabbara. L; Flemming, S.; Nickisch, IS.; Neh, H.; Westermann, J. Synlett, 1994, 679 Et2Zn , MeCN , 1.5% NiC12 , -3OOC phLph309’ chual pyrrolidine 0*Phuh 75% (82% ee , S)Asami. MJ Usui, K.; Higuchi, S.; Inoue, S. Chem. L&t., 1994,297Compendium92PhSection 74Eof Organic Synthetic Methods, Vol9LiY CH2CI;!99% AI(OAr)3 , -78OC , lhAr = 2,5diphenylphenyl Maruoka,PhK.; Shimada, I.; Imoto, H.; Yamamoto. H, Synlett, 1994, 519 PhMezSi0 HSiPhMe2 , toluene , 1 10°C A-N[Rh2(oAc),ldNJlI I Bn Bn u T,; Oda, T.; Kimura, F.; Onishi, H.; Kanda, T.; I(;ito. S, J. Chem. Sm. Chem. Commun., 1994,2143 1. PhMe#Li ph&C02MeCrump, R.A.N.C.; wing.;87%, Me$Zn , THF/toluene , O°C2* aq* NH4C1CO2Me98% 73% using cuprate Urch, C.J. .I. Chem. Sot., Perkin Trans. l., 1994, 7015% CuBr , THF , TMSCl ,4h AlMe, 10% solution in hexane96% Kabbara. J,; Flemming, S.; Nickisch, K.; Neh, H.; Westermann, J. Chem. Ber., 1994, 127, 1489 t-But-Bu (t-Bu)2Cu(CN)Li2t-Bu wC02Et Gerold, A.; .Krause. N, Chem. Ber., 1994, 127, 1547quant. 111111111 CO2EtSection 74EConjugate Alkylations93, DME ,0.3h-AC02EtLiOH , Hz096% FJ Forcellese, M.L.; Locati, L.; Screttri, A.; Scolamiero, C. Guzz. Chim. Ital., 1994,124,467PhBr, NiBr2, e’ *-/c”u63%phwco2Et3 H20, DMF-Py , 80°C Bumr , Bu&I Condon-Guegnot&; Leonel,E.; N&l&ec, J.-Y.; P&ichon,J. J. Org. Chem., 1995, 60, 7684 OSiMe30 5 M LiClOd, etherSarawathy,V.G.; Sankararaman.J.70% Org. Chem., 1995, 60, 5024t-BuZnBr , THF/pentane, -3OC 2 TMSCl , 1.5BF3aEt2 Hanson,M.V.; Rieke,J. Am. Chem. Sot., 1995, I 17, 10775iPr1, Bu$nH , Yb(OTf)3CH2Q/hexaneKHF . . Slbl. M&; Jasperse, C.P.; Ji, J. J. Am. Chem. Sot., 1995, II7, 10779 neatAl(C3H7)3,5% CuBr Ph& w;Flemming,S.; Nickisch,K.; Neh, H.; Westermnn,J. Tetrahedron,76% 1995, 51, 74394Section 74FCompendium of Organic Synthetic Methods, Vo191. &D,O”C,hv2. LTA , PhH , heatBarton, D.H.R.; Chem, C.-Y.; Jaszberenvi. JCs, Tetrahedron,1995,C02Me 98~25% 51, 1867R.-S)61%(80%ee;10:90Wu, J.H.; Radinov, R.; Porter. N.A, J. Am. Chem. Sot., 1995, 117, 11029 REVIEW:“Intramolecular MichaelandAnti-MichaelAdditionsto Carbon-Carbon Triple Bonds,”Rudorf, W.-D.; Schwarz,R. Synlett, 1993, 341 SECTION74F:Cyclopropanations, SO2Phincluding Halocyclopropanations‘CH(SOMe)2,DMSO 99% 20°C, 15minJ-E,; Lofstom,C.; Juntunen,SK. Tetrahedron Lett., 1993, 34, 2007 N2CHC02t-Bu, CH2C12/,%, + ,,+’A *,%, ‘Cod-Bu ‘h ‘C02t-B u . (86 . 14) 75% 92%ee Ito, K.; Katsuki.T, Tetrahedron Lett., 1993, 34, 2661 CuOTF-biarylamine ligand -,PPC&I, CrCl$Fe02Et C02EtHu. C-M.; Chen,J. TetrahedronLett., 1993, 34, 595789%Section 74FCyclopropanations9570% Kreif. A; Dubois, P. TetrahedronLett., 1993, 34, 2691PhP Bu$nN(Et)CO2Me,DCE(93:7 1,2-tranxcis) Shibata,I; Mori, Y.; Yamasaki,H.; Baba,A.; Matsuda,H. Tetrahedron Lett., 1993, 34, 6567Phbis-Rh catalyst, styrenet 0 . Davies.;L4 = = Eo,?Me63% Hutcheson,D.K. TetrahedronPh +9O%eeLett., 1993, 34, 72431.NBS, DMSO ,5 min ,,il/v/::::;:Hp Kd’Dechoux,L.; Ebel, M.; Jung,L.; Stembach.J.F, TetrahedronL”ToEt 10%Pd(PPh3)4,DMF ,7hH g2%(>99: 1 cis:trans)Lett., 1993, 34, 74050 Ogoshi,S.; Morimoto, T.; Nishio, K.; Ohe, K.; Murai. S,J. Org. Chem., 1993, 58, 9gg%96Compendium of Organic Synthetic Methods, Vol9..(97Section 74F3)84%avres.H.ML; Huby, N.J.S.; CantrellJr., W.R.; Olive, J.L. J. Am. Chem, Sot., 94681993,115,CrC12- DMF ,3h BuCHO 32%Montgomery,D.; Reynolds,K.; Stevenson.P,J. Chem. Sot. Chem. Commun., SO2PhLiCH(SPh)S02Ph,THFSPh-78OC + O°C1993,363PhS Isc-81% Bailey, P.L.; Hewkin, C.T.; Clegg,W.; kkson. R.F.W, J. Chem. Sot., Perkin Trans. I., 1993,577Me [email protected]+%H(C02Me)2,TI-IF-HMPA -70OC + O°C ,3hC02Me 63%Watanabe,Y .; Ueno,Y .; m.T, Bull. Chem. Sot. Jpn., 1993, 66, 2042 CH212,Zn , Et20 40°C, 8h Pb , Me$iClSK.;Kakiuchi,T.; -0.Ic J. Org. Chem., 1994, 59, 267197%Section 74FCyclopropanations97PhS,b @Ylr::~~~: 302Me Mac 50%C02MeDenis,R.C.; Gravel. D, Tetrahedron Lett.,35, 45311994,(2.7 OHBu$n ai2 [email protected], CH& CH$lz-hexane, -2OOC NHSO&H,pNo,BGn, -%, /#H ++HA_OH+ NHS02-C6H4p-NO286%ee(2S,3R),94% Imai, N.; Sakamoto,K.; Takahashi,H.; Kobavashi,S, Tetrahedron Lett., 1994, 35, 7045 1. PhCHN2 2. PhCH=CHz, rt , 12hcp OC-Fe/ oc-4Seitz, W.J.; Hossain.M.M, Tetrahedron80% (96:4 cixtrans) Lett., 1994, 35, 7561MezNPh&pNMe2 + “)71. PheOHPh0/0 B Buw PhvOH2.2.2 Zn(CH21)2 >95%(29:1)Charette.A.B,; Juteau,H. J. Am. Chem, Sot., 1994, 116, 2651 Et$n , CH212,CH& hexane, -2OOCPh aPh-oHHs s: a H,SO,PhOHN ,B-iBu N ‘SOquant.(76%ee) PhImai, N.; Takahashi,11.;Kobayashi.S, Chem. Lett.,‘1994,17798Compendiumof Organic Synthetic Methods, Vo19Section 74FPh Ph ’ [email protected] +C&03, 7o”c DME , trace waterPhMe3SiY.-z;..8) 93% MesSi Tang, Y .; Zhou, Z.-L.; Xia, W.; Shi, L.-P. J. Chem. Sot., Perkin Trans. I .,1994,8933-pentanone/LDA ,THFS02Ph Ericsson, A.M.; Plobeck, N.A.; mkvall.62% J.-E. Acta Chem. Stand. B., 1994, 48, 252Zn ClMe2SiCH$H$iMe2ClMo(.herwell.W.B,; Roberts, L.R. TetrahedronL&t., 1995, 36, 11212 Ti(OiPr)d 4 iPrMgBr -45OC +0°C 93% (58:42Kasatkin, A.; Sate.PhaOHTetrahedronLat., 1995,36,trans:cis)6079l.Zn(CH$)2 2. -78OC -+ -2OOC 3. TiQph-YoH 90%Charette.,Brochu, C. J. Am. Chem. Sot., 1995,117, 11367Section 75Alkyls from Misc.995% semi-corrin Cu complex , DCE 23OC57% (95% ee) Pique, C.; Fahndrich, B.; pfaltz. A, Synlett, 1995, 49 1 1. XX12 , CC14, reflux 2. NaI04 , 0.1 RuC1385%3. Li 5% DTBB , THF 4. H20 Guijarro, D.; Yus. w Tetrahedron,ArAr = 4- t-bu tylphenyl 1995, 51, 11445REVIEW:“The AsymmetricCyclopropanantion of Acyclic Allylic Alcohols:Efficient Stereocontrol with IodomethylzincReagents,”w. A&; Marcoux, J.-F. Synlett, 1995, 1197SECTION75:ALKYLS, METHYLENES AND ARYLS MISCELLANEOUS COMPOUNDS~co2MhMe#-~-~~2~(OAc)~as.LEMeY,; Planchenault, D.; Weber,V. Tetrahedron Lett., 1994, 35, 9549SOzt-BuFROM73%Ph2 PhMgBr,5% NiC12(PPh&77%Clayden,J.; Cooney,J.J.A.; Julia. M cJ. Chem. Sot., Perkin Trans. 1.) 1995, 7 REVIEW:“OrganonickelChemistryin OrganicSynthesis.SomeApplicationsof Alkyl and MetalacyclicDerivatives,”C&npora,J.; Paneque, M.; Poveda,M.L.; Carmona.E. Synlett, 1994,465Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)100Compendium of Organic Synthetic Methods, Vol9CHAPTERPREPARATIONSECTIONSection 77OF AMIDES76: AMIDESFROM ALKYNES 0.3 Iu1&0)16, co, Hz0 dioxane , NEt3 , 175OC Ph PhHirao, K.; Morii, N.; Joh, T.; Takahashl. . S, TetrahedronSECTION77: AMIDESFROM ACID DERIVATIVES 1. SnFJ(TMS)2]2OH Bumell-Curty,2.C.; lXosw Tick,Lett., 1995, 36, 6243, THF , rt PaNNH‘N7 14h89%TetrahedronLett., 1993, 34, 5193Li , Me3SiCl CsF’N2pANHiplq.llKawaguchi,C&I17NH2, W-J17CWH180°C, 30 min t C8h. SIC. B&;77% M.; Hamaoka, S.; Mori. M. Tetrahedron L&t., 1993, 34, 6907NHC8H1798% Zdravkovski,2. Synth. Commun., 1993, 23, 276111%Section 78Amides from Alcohols101ClPhNMM , PhCl , mrcrowave *N75OC ,2 minMe(20 Bose, AK.; Banik, B.K.; Manhas. MS, Tetrahedron80) no yieldLett., 1995, 36, 213 PhPhCH-NPh , toluene , Bufl 40% (5:95 cis:trans) Ph Browne, M.; Burnett, D.A.; Caplen, M.A.p; Chen, L.-Y.; Clader, J.W.; Domalski, M.; Dugar, S.; Pushpavanam, P.; Sher, R.; Vaccaro. W,; Viziano, M.; Zhao, H. Tetrahedron Lett., 1995, 36,2555 -C02H,CWl;!‘z ;;iPPb. Frayen. P,Synth.bCONHBn98%Commun., 1995, 25, 959 1. NsCl , NEt3 , DMAP/MeCN, rtPhCOOH 2. PhNH;! , rtNHPhIs,e. JC,; Cho, Y.H.; Lee, H.K.; Cho, S.H. Synth.Commun.,SECTION78: AMIDES OHFROMALCOHOLS1995, 25, 2877AND THIOLSCoC12, Ac20, MeCN *Mukhopadhyay,M.; Reddy, M.M.; Maikap, G.C.; w.-(=)-/OHMeCN , BFyOEt2Firouzabadi.LNHAcJ, J. Org. Chem., 1995, 60, 2670w-H,; Sardarian, A.R.; Badparva, H. Synth. Commun., 1994, 24, 60192%102Section 81Compendium of Organic Synthetic Methods, Vol9SECTION79: AMIDESFROMALDEHYDESNO ADDITIONAL EXAMPLESSECTION80:AMIDES ARYLS‘-(=)FROMALKYLS,PPA , AcOH , NH20H*HClMETHYLENESAND‘-0llO°C , 14h80% Cablewski,T.; Gurr, P.A.; Raner,K.D.; SSECTION81: AMIDESFROMOrg. Chem., 1994, 59, 5814C&J.AMIDESConjugate reductions of unsaturated amides are listed in Section 74D (Alkyls from Alkenes).oJ-q// 1,,,,,,, A HWei, Z-Y.; Knaus.TetrahedronLett., 1993, 34, 44392.1 TBSOTf ,23OC 4.2 NEt3 , 1.75hPh JR *N/ IPhd/MeMe 75%2.1 TBSOTf ,23OC 4.2 collidine ,2h&&91% (>99%ee)MeOHPhJ 49%G.E.; McHardey,S.F.; Murry, J.A. TetrahedronPhI(OAc)2,A! IKOHN/MecH2oTBsLett., 1993, 34,621572% NHCO2MeVaid, R.K.; P&ash, 0.; Tuladhar,SM. J. Org. Chem.,Section 81Amides from AmidesPhMgBr , THFOEt H Wei, Z.Y.; Knaus.Ph10378%Org. Prep. Proceed. Int., 1993, 25, 2551. 2 eq. s-BuLi, (-)-sparteine NHMe 2. Me1Beak. P,; Du, H. J. Am. Chem. Sot.,NHMe 84%(78%ee)1993,115, 25164.2 eq.CuBrz*LiOt-Bu77%Ph rt ,6h NH2 Yamaguchi,J.; Hoshi,K.; Qkgla. T, Chem. Lett.,5) c>, 01993,PhHNJLOt-Bu1273, acetone, O°CCL N N 0 I I H OH Nesct,S.M.; Benneche,T.; Undheim,K. Acta Chem. Scand. B., 1993, 47,71% 0 1141CF3S03H, CH2C12 H0.75h , 20°CC.&l,; Fallah,A. Tetrahedron&-HLett., 1994, 35, 293DkE4-K;DIAD = diisopropylazodicarboxylate 0 Ww.M.A. TetrahedronLett., 1994, 35,66591% (+ 4% lactone)104Compendiumof Organic Synthetic Methods, Vol9Section 8 11. Br;! 2. NEt3 3. BnNH2n B N4. Mg(OMe)ztier.P,; Dogan, 0.; Pillai, S. TetrahedronLett., 1994, 35, 1653Axon, J.; Boiteau, L.; Boivin, J.; Forbes, J.E.; md.Hoffman.V,; 35,323l(s)*Y 86×79%1. (PhCO)zO , PhH , reflux 2. Bu$nH , AIBN , PhHBnI-IN, MeOH02MeMe67%x”high yield” Lett., 1994, 35, 1719SZ, TetrahedroniPrOH , 80°C, lhd I OTf Nayyar, N.K.; Shankweiler,CH20iPr 85%J.M.; KlinekoleH III, B.W. TetrahedronC7H &HO, Hz, 40 bar Pd/C-Na2S04, EtOAc1ooOC H Fache, F.; Jacquot, L.; J,eme.Ph-NVCI93%w17M, TetrahedronL&t., 1994, 35, 3313s-BuLifIMEDA I BocLett., 1994,, THFPh 4-78OC, 5hBeak. P,; Wu, S.; Yum, E.K.; Jun, Y.M. J. Org. Chem., 1994, 59, 276N I Boc82%Section 81Amides from Amides105PhCHO , PPE , 60°C, 16hH N’51% * I PPE = polyphosphoric ester ci Ph Marson. CM,; Grabowska, U.; EaIlah, A.; WaIsgrove, T.; Eggleston, D.S.; Baures, P.W. J. Org. Chem., 1994, 59, 291 NH2S Me N’1. 1.3 eq. POC13,-78OC2.3.5 eq. TM&S, -78OC +Me N’ rt ,4h91%* c ei Smith, D.C.; Lee, S.W.; Fuchs. P.L, J. Org. Chem., 1994, 59, 348 0BnNH2, AlC13 , 90°C >NHBnNH267% Bon, E.; Bigg. D.C.H.: Bertrand. G, J. Org. Chem., 1994, 59, 4035yx N I1.2 s-BuLi/2 TMEDA THF , -78OC, 8h Ot-Bu2. BuICH3Snieckus. V,; Rogers-Evans, M.; Beak. P,; Lee, WK.; 1994, 35, 40670 -YA N Ot-Bu I CH2Bu 70% Yum, E.K.; Freskos, J. Tetrahedron L&t.,Bu$nH , cat. AIBN (addn over 4 h) degassed cyclohexane -(DoPh Callier, A.-C.; Quiclet-Sire,B.; Zard. S.2, Tetrahedron66% Lett., 1994, 35, 6109Me106Compendium of Organic Synthetic Methods, Vol9Bu$nH,Section 8 1AIBNPhH (OSM) Keusenkothen,P.F.; Smith. M.B, J. Chem. Sot., Perkin Trans. I., 1994, 2485Ts I NiPrMgC1, THF , O°C ,6h/4J4 *‘Ph. . oshlmuu. 3465. 57) 63% (45 A, ; Abe, H.; Hirosawa, C.; Tamao, K. J. Chem. Sot., Perkin Trans. I., 1994,anek- E,; Wuonola,M.A.;NH2Harlow, R.L. J. Heterocyclic65% x low yield Chem., 1994, 31, 1251 H I NN1. B tCH20H2. CH2=CHCH2SiMc3 BF3eOEt2 63% 0 R… menko. A.V.. . La n g. H, J. Org. Chem., 1995, 60, 4002 a V-bhBr OMeN’ IBu$nH , AIBN , PhH reflux ,8h (syringe pump, 7h) *~;~;NHco2Mx;:~ 2co$k 30%Lee.;Whang,I-IS.; Chung,C.K. TetrahedronMt.,1995, 36, 913360/ 0co2MSection 8 1Amides from Amides-L(BnNEt&MoQ107, CHg1282%Ph-78OC * rt ,30 min me2 Ilankumaran, P.; Ramesha, A.R.; Chandrasekaran. S, Tetrahedron L&t.,me21995,36, 83111.2.2 eq.BuLi , THF , -78OC+ 0°C 0 2.PhN’ I dNHMe 43. H30+ 4. Me$iCl , NaI , MeCNWY. Pts, TetrahedronLett., 1995,MePhPh 75%x92%36,4932 SnC12,2KI CH2C12 , rt , 12h N-(f6Hll53% + 10%benzophenone QmokaT,; Iwama, T. TetrahedronLett., 1995,36, 5559HC=CCH2Br,DMWDMF , NaH LiBr , O°C + rt THPO Liu, H.; Ko, S.-B.; Josien,H.; Curran.D.P, TetrahedronLett., 1995,36, 8917PhPh PhMn(OAc), AcOHD’Annibale,A.; Resta,S.; Trogolo,C. TetrahedronLett., 1995,36, 903987%108Compendium42of Organic Synthetic Methods, Vol9Section 822% Rh#SMEPY)4 0cwktN -bY Doyle. M.P,; Kalinin,70% (96% ee)cm2A.V. Synlett, 1995, 1075 SPhMeS&SPhneat, rt Id Ar = 4-methoxyphenyl66%Ar . x; Nakaharu, T.; Nishimura, M.; Nishikawa, A.; Kameoka, C.; Ikeda, M. Tetrahedron, m. . 1995, 51, 2929 Ph Bu$nH, PhI AIBNPhtoluenhe , refluxMe bileMe47% 12% Sato, T.; Chono, N.; Ishibashi, H.; Ikeda. M, J. Chem. Sot., Perkin Trans. I., 1995, [email protected] ,SO2TolPhPhMe$GCHC02Et41%N -7. u-. UJt;SECTIONb/ TolO# Arora, A. J. Chem. Sot., Perkin Trans. I., 1995, 260582: AMIDESFROMAMINESNaB03a4 HfiP L -N-Ph Nongkunsam,C02Me, CF3C02H80°CP.; Ramsden. CA, TetrahedronLett., 1993, 34, 6773N Ph 51%PhSection 82Amides from Amines109NHBnSn[NUMS)212 9hexme 9fi CO2MeC3Hpivalic acid5rC3H7NBn89% Wang, W.-B.; wJ. Am. Chem. Sot., 1993, 115, 9417 NCCH2CH0,c8H17-NH2Duetsch, J.; Niclas. H.-J,Synth.r-t, 6h) C&I 17-NHCH0 Commun., 1993, 23, 156178%1. N-cyclohexyl-N’,N’,N”,N”tetramethylguanidine , pyridine toluene , CO2 , – 10°C 2. toluene , SOCl;! , -1OOC 77% McGhee. W.D.; Pan, Y.; Talley, J.J. Tetrahedron1. 2eq.Let?., 1994, 35, 835R pkPhP Cl3eqNEt3,THF67%2. excess NaH Osbom, H.M.I.; Cantrill, A.A.; Sweenev. J.B.; Howson, W. TetrahedronLet?., 1994, 35, 3159xylene , 150°C, 3h NHBn -Gee.c), N I Bn0 93%DLL; Ramaseshan, M. Synlett, 1994, 743ocNHBnCO, MeCN Pd(PPh3)4, NBu3OTfQiso. G.T,; Meyer, A.G. Tetrahedron,quant. 1995, 51, 5585110Compendium of Organic Synthetic Methods, Vol9C3H7wmt*co [email protected] )Section 83C3~7Aqqmt2 0b&&&.. S.-L; Imada, Y.; Nishimura, K. Tetrahedron,SECTION83: AMIDESFROM78%1994, 50, 453ESTERS ,0C02t-B uH-N moAcOCOzt-BuC02t-BuK2CO3, IT, IdmNxC02t-Bu77% . J-P,; Thorimbert,S.; Touzin, A-M. TetrahedronL&t., 1993, 34, 11592 eq.Sn[NTMS2]2 2 eq.Me2NCH2CMe20H Ph-CO2Me2 eq.PhCHMeNH2dyA HWang,W.-B.; Restituyo, J.A.; Roskamo. E.J, TetrahedronPh LA1.5SnFJ(TMS)& , THF0 OMe97%L&t., 1993, 34, 72171.5Et2NHaHCl,rt , 18hPh 3mt252% Smith, L.A.; Wang, W.-B.; Burnell-Curty, C.; Roskamn.E.J, Synlett, 1993, 850 0iPrNH2, t-BuOH ,1.5d 0-Chen.S.-T; Chen,S.-Y.; Chen,S.-J. Tetrahedron 0 C3H7A25OCI HNaEtzAl(Bn)z, toluene OEtreflux , lh69%Lett., 1994, 35, 35830 * C3H72NHBn 93%Sim, T.B.; Yoon. N.M,SynZett,1994, 827Section 85/ PMPAmides Tom HalidesPhI N111(Lp+(;p2. NEt3 , CH2C12PMP = 4-methoxyphenyl. 30) 99% (70 Annunziata. R,; Benaglia, M.; Cinquini, M.; Cozzi, F.; Ponzini, F.; Rimondi, L. Tetrahedron, 1994, 50, 29390 A1. BC13-SMe2 SPYPh/ip-l =-MePhNMe274% (78%ee)2. O*ph3N-PMPPMPPMP = N-4methoxyphenyl Annunziata,R.; Benaglia,M.; Cinauini.M.: Cozzi. F, Tetrahedron Lett., 1995, 36, 613SECTION84:AMIDES FROM THIOETHERSETHERS,EPOXIDESANDNO ADDITIONAL EXAMPLE!3SECTION85: AMIDES Br SiMe3FROMHALIDES1.MgAND SULFONATES2. PhNCO83%Co& Jr.. M.P,; Pollock, C.M. J. Org. Chem., 1993, 58,-MgBrc1’NMe2+ bme2cat. NiClz(dppe), THF vrt Babudri,F.; Fiandanese, V.; Marchese.G,; Punzi, A. Synlett,1994,71990%112Compendium of Organic Synthetic Methods, Vo19Section 871. CS2, THF PhMgBr2. BtS02CF363%3. BuNI&. ~A.R.;SECTIONBt = benzotriazol-l-y1 Moutou, J.-L.; Yang, 2. Synlett, 1995, 9986: AMIDESFROMNHBuHYDRIDESNO ADDITIONAL EXAMPLESSECTION87: AMIDESFROMMe02C-aldehydes canalsobe usedKETONESNH2TEA, N~BH(OAC)~ DCE , rt ,45h00-b 92%bdel-Manid. A.F,; Harris,B.D.; Maryanoff, C.A. Synlett, 1994,81 OTIPS1. 10eq.TMSN3 2 eq.PPTS CH2C12,rt ,2d 2. UV , 0°C , lh 79~89%Evans. P.A%;Modi, D.P. J. Org. Chem., 1995, 60, 6662Milligan, G.L.; Mossman,C.J.; Aube, J. J. Am. Chem. Sot., 1995, 117, 104491. NI$OSO3H, SiO2 2. Hz0 , microwave Laurent,A.; Jacquault,I?; Di Martino, J.-L.; Hamelin.J, J. Chem. Sot. Chem. Commun., 1995, 1101Section 89Amides from AlkenesSECTION88: AMIDESFROM113NITRILESUHP , cat. K2CO3 , aq. acetone NPhCNrt, lhUHP = urea-hydrogen peroxide adduct Balicki. R,; Kaczmarek, L. Synth. Commun., 1993, 23, 3149 HMn02, SiO2, hexaneCN P Breuilles,P.; Leclerc,R.; m.rt,lodD, Tetrahedron92%PuLett., 1994,NH235,1401 0Al203 (neutral), 60°C, Id70%CNt * w NH2 Wilgus,C.P.; Downing,S.; Militor, E.; Bains,S.; Pagni. R&k: Kabalka. GW, Tetrahedron Lett., 1995, 36, 3469SECTION89: AMIDESFROMALKENESTsN=IPh, Mn salencatalyst * PhA Ph pyridineN-oxide, MeCN , rt Noda, K.; Hosoya,N.; Irie, R.; Ito, Y.; Katsuki. T, Synktt, 1993, 469 1. PhI=NTs, Cu(OTf)2, MeCN e 2.0.1 M NaOHTs34%N-TsN d-77%JCL; Muldowney, M.P. Synlett, 1995,949SECTION90:AMIDESFROMMISCELLANEOUSCOMPOUNDSBnN=C=O, hv (Pyrex filter) @42% cr(m3v. J.H.; Ahmed,G.; Ferguson,M.D. TetrahedronL&t., 1993,34, 5397114Section 90Compendium of Organic Synthetic Methods, Vol9o=Bu&Re04,N-OHCF$03H,MeNO50% H2NOHaHClNarasaka, K.; Kusama, H.; Yamashita, Y.; Sato, H. Chem. Lett., 1993, 489)iic,T”Sy+ a2STMSOTf,CH; 7202n=aux,O,PhPhPouilhes,A.; Langlois.Y,; NshimyumuKiza, P.; Mbiya, K.; w.30% (>95:5enbexo) 1,. Bull. Sot. Chim. Fr.,1993, 130, 3049 //O0//2. 1. MeMgCl BEt3 *Ph’3. H2NOS03H Me Huane..-C,; Reinhard,E.J.; Reitz, D.B. Tetrahedron0 50%PhHs NH2Mt., 1994, 35, 7201hv , hexane, PhNMe2ipmaJ( = 0.77 Post,A.J.; Nwaukwa,S.; Morrison. H, J. Am. Chem. Sot., 1994, 116, 6439CO, MeOH, Pd(dpppK129PhH K2C03,160°CNHCOzMe 59%MeO$HN02NReddy,N.P.; Masdeu,A.M.; El Ali, B.; Alner. H, J. Chem. Sot. Chem. Commun., 1994, 863Section 90AProtection of AmidesPh. 70 Mn(tpp)Cl, MeCN3o”c115Ph.* P0 60% tPP = tetraphenylporphyrin Suds. K,; Sashima, M.; Izutsu, M.; Hino, F. .I. Chem. Sot. Chem. Commun., 1994, 949 MontmorilloniteN-OHK-10, microwave *NHPh7 minBosch, A.I.; de la Cruz, P.; Diez-Barra,(17% with heating and no microwave) E.; Loupy, A.; Langa. F, Synlett, 1995, 1259DMF , POC13, 90°C ,.N-OH Majo, V.J.; Venugopal,CHO0 M.; Prince, A.A.M.;N-OH60% Perumal. P.T, Synth. Commun., 1995, 25, 3863 H N0.2 Bu$lRe04,0.2 CF$OsH MeNO*, reflux ,0.5 NH~OH~HClPhx>”CJ Ph Kusama, H.; Yamashita, Y.; Narasaka, K. BuZl. Chem. Sot. J’n., 1995, 68, 373SECTION90A:PROTECTION91%OF AMIDES0 02 Mn(OAc)3.2 H20, EtOH CU(OAC)~~H~O, 55OC 45%N4N4 SiMe3OH Ghosh, A.; MiI&r. MuI TetrahedronL&t., 1993, 34, 83SiMe3116Compendiumof Organic Synthetic Methods, Vol9Section 90A1. AlC13 ,6O”C 2. PhOMe ,6hKim, J.N.; Ryu. E.K, TetrahedronMg(ClO&Boc P Stafford.=; 7873Lett., 1993, 34, 356799% 50°C ,20h * PA NHMe r’ Me Brackeen, M.F.; Karanewsky, D.S.; Valvano, N.L. Tetrahedron L&t., 1993, 34,Mg(OMeh P, MeCN, MeOHCO$-Bu Wei, Z.-Y.; Knaus.J TetrahedronP -0 +90%Lett., 1994, 35, 545 5 eq. Ac20,4% 2.2 eq. Bu$nHPd(PPh& , CH2C12NHOMe AcHN * G 58% o Roos, E.C.; BernaM, P.; Hiemstra, H.: Speckamp. W-N,; Kaptein, B.; Boesten, W.H.J. .I. Org. Chem., 1995, 60, 1733 rt , 10 minCompendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)Amines from AlcoholsSection 93CHAPTERPREPARATIONSECTION91: AMINESOF AMINESFROMALKYNESNO ADDITIONALSECTION92: AMINESoxSECTION11793: AMINESFROMACID DERIVATIVESNO ADDITIONALFROM 1. MeLi,EXAMPLESEXAMPLESALCOHOLSAND THIOLSTHF2. PhCN , warm OH Fitzgerald, J.J.; Michael, F.E.; Qlofson. R.A. Tetrahedron(J-JPh47%L&t., 1994, 35, 9191 Me1. BuN3, 2.5 eq. TfOH 95% 2. NaBH4 mn.W.R,BuFang, W. J, Org. Chem., 1995, 60,496O PhCH2NHTf, DEAD,PPh3PhCHzOH 93% Bell, K.E.; Knight. D.W; Gravestock, M.B. Tetrahedron==c OHLett., 1995, 36, 8681HNBn2, SnC12, [email protected], THF ,2dw NBn22% Pd(PPh3)4, 50°C70% Masuvama.Y.; Kagawa, M.; Kurusu, Y. Chem. L&t., 1995,1121Compendium of Organic Synthetic Methods, Vol9118SECTION94: AMINES Me3S’PhCHOFROMALDEHYDES-3Me3SiCl ,29hJahn, U.; Schroth. W, Tetrahedron(tSection 94Lett., 1993,34, 58631. C$I 1lCHO , BER , EtOH NH2Et3NHCl 2. BER , NaOH* o-NHCH2C5H1 lBER = borohydride exchange resin Yoon. N.M.; Kim, E.G.; Son, H.S.; Choi, J. Synth. Commun., 1993, 23, 1595 LiAl(NHBn)d,89%ether25OC, 7h Solladie-Cavallo.A,; Bencheqroun,M.; Bonne, F. Synth. Commun., 1993,23,16831. Bzt-SNH2 , NaOH , EtOH 2. PhSN(TMQ, cat. TBAF , THF Ph3. Bu$nH-?B&in,, cat. AIBN , cyclohexaneCHO61x69%J.; Fouquet, E.; Zard. SZ, Tetrahedron,1994, 50, 17451. Me2NH*HCl, Ti(OiPr), EtOH ,25OC, 10h, NEt3 *ph-CHO 2. NaBH4,25OC Bhattacharvva,PhCHOS, .I. Org. Chem., 1995,PhwNMe2, 10h95%60,49281. BnNH2, PyeBH3, MeOH MS 481,16hPh/N-Ph2.6NHCl 3.8 N NaOH Bomann, M.D.; Guch, I.C.; DiMare. M, J. Org. Chem., 1995, 60, 5995 TsNH2, Si(OEt), , 160°C, 6h > PhCHO Love. BE; Raje, P.S.; Williams II, T.C. Synlett, 1994, 493PhCH=NTsI H87%68%Section 96119Amines from AmidesBnNH2 , Bentonite , rt ,3hPhCHO80%PhCH=N-Bnketones can also be used Saoudi, A.; Benguedach, A.; Benhaoua. H, Synth. Commun., 1995,25,2349 Related Methods: Section 102 (Amines from Ketones)SECTION95:AMINES ARYLSFROMALKYLS,METHYLENESANDNO ADDITIONAL EXAMPLESSECTION96: AMINESFROMAMIDESC6Hl3Fisher, G.B.; Fuller, J.C.; Harrison, J.; Goralski, C.T.; Sin Tetrahedron Lett., 1993, 34, 1091R,KH , THF , Cp2ZrHC1JyClOH21 tPhJL-2OOC + rtPlrJNwoH2186%Schedler, D.J.A.; Godfrey, A.G.; Ganem, B, Tetrahedron Lett., 1993, 34, 5035 1. LiHMDS ; BnBr 2. LiHMDS ; Me1 3. LiA1H4 4. H2, Pd-CG? Ph 0 Westrum, L.J.; Meyers. A& Tetrahedron+ H’ 89%Lett., 1994, 35, 973Ph Tic13 ,3 eq. CsK PhFs90% H A; Hupperts, A.; Ptock, A.; Janssen, E. J. Org. Chem., 1995, 60, 5215120Section 97Compendium of Organic Synthetic Methods, Vol9HBr ,163OCH-Nw-phNI-IPheHBrL-l88% Poindexter. Cr.&; Bruce, M.A.; LeBoulluec, K.L.; Monkovic, I. Tetrahedron L&t., 7331 /sWF31994,35,t-BuLi , THF , -60°C, 3h t-Bu52% Bozee-Ogor, S.; SaIou-Guiziou, V.; Yaouanc, J.J.; Handel. H, Tetrahedron L&t., 1995, 36, 6063 Ph 3 Ti (powder), THF, 21h 3 TMSCl , refluxPhAN-(PhH r. pL; Hupperts, A. J. Am. Chem. Sot.,1995,117,4468H I30%H202, AcOH, 25OC wMe Grivas, S.; Ronne, E. Acta Chem. Scand. B.,1995,49,H n-N Me85%225Related Methods: Section 105A (Protection of Amines)SECTION97: AMINESN -PhAImena, J.; Foubelo, F.; mFROMAMINES1.5 Li (powder) , TI-IF cat. CteHs , -78OC, 6h 2.H20 M, Tetrahedron* vNHPh 93%Lett., 1993, 34, 1649Section 97Amines from AminesPhCHO , TFAMe H121Et$iH , CH2C12, O°C83% HAppleton, J.E.; Dack, K.N.; Green, A.D.; Steele. J, TetrahedronL&t., 1993, 34, 15299-BBN , THF ,20h *Wy-”56%H ‘Ar Ar = 3,4-dimethoxyphenyl Gaul, M.D.; Fowler, K.W.; Grieco. P.A, Tetrahedron L&t., 1993, 34, 309970%2. H30+ Maye, J.P.; Nerrishi. E. TetrahedronL&t., 1993, 34, 3359?hPh I/ 0 hA 10 eq. MeLi, PhH ,5O”C w-I v H’I vI-YNH2Y >60% Genin, M.J.; Biles, C.; Romero&D.L, TetrahedronMt.,20% 1993, 34, 43011. s-BuLi , TMEDA 2. Me13. s-BuLi, TMEDA * Mz&’cx N 4. Me1 I Boc I&&. P,; Lee, WK. J. Org. Chem., 1993, 58, 110962×41% NI BocMe122Compendiumof Organic Synthetic Methods, Vol9Section 97t-Bu 1.1.5 LDA, THF , O°C 62%THF, 15h , O°C + rt 3.3 eq. K2CO3, MeOH heat, 3h N.G,; Keppens, M.A.; Stevens, C.V. TetrahedronLett., 1993, 34,46932.5 eq. LiBHEt3 , THF , rt 84% (1:l cixtrans) Blough, B.E.; Carroll, F.I. TetrahedronI H Kanth, J.V.B.; Pemv.aI/NH2H L&t., 1993, 34, 72392.PhBr,THF,rt,6h l.Li,THF 3. MeOH ; 20% HCl MJ.86%N I PhOrg. Chem., 1993, 58, 3156 H I5% Pd(OAc)2, 5% PPh3 100°C ,3.5d, Na2CO3 +65, ’ * Larock. R.C,; Berrios-Pefia, N.G.; Fried, C.A.; Yum, E.K.; Tu, C.; Leong,W. J. Org. Chem., 1993, 58, 4509 IONMe1. w&r95% 36, 7357Section 105ACLProtection of Amines139, DCE , refluxN Me 2. MeOH, reflux I Bn Yane. B.V,; O’Rourke, D.; Li, J. Synlett, 1993, 195TiC13-Li , THF , reflux ,22h Me2NBn c, Talukdar, S.; Banerji. A, Synth. Commun., 1995, 25, 813(R74% N I HMe2NHMe55%Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)140Section 107Compendium of Organic Synthetic Methods, Vol9CHAPTERPREPARATIONSECTIONOF ESTERS106: ESTERS FROM ALKYNES OHxylenes , 150°CH OEt~ 72%OH Liang, L.; Ramaseshan, M.; MaGee. D.1, Tetrahedron,SECTION1993, 49, 2159107: ESTERS FROM ACID DERIVATIVESThe following 1. 2. 3.2xtypes of reactions are found in this section:Esters from the reaction of alcohols with carboxylic acids, acid halides and anhydrides. Lactones from hydroxy acids Esters from carboxylic acids and halides, sulfoxides and miscellaneous compounds 0 0tiI0 Li [Binol-AlHOEt] -78OC +, THF rt -0 Matsukl.;.(84% e-e)Inoue, H.; Takeda, M. Tetrahedron CO2I-rI tiLett., 1993, 34, 1167PhCHzOH ,2,6-lutidine Ck/ Cl 00SfNClFolmer, J.J.; Weinreb. SM, Tetrahedron9 C&C12-78OC + rt Lett., 1993, 34, 2737C02CH2Ph81%69%SectionEsters from Acids107141Si( iPr),90°COH Soderauist, J.pL; Miranda, E.I. Tetrahedron Lett., /0-S 1993,34,4905C02HTEOA = triethyl orthoacetate Trujillo, J.I.; Goaalan.AS, Tetrahedron Lett., 1993,i(iPr)393%C02Et735534,C&[email protected] , TsOH, neat PhC02Hmy.PhC02C8H17 97% microwave,3 min A,; Petit, A.; Ramdani,M.; Yvanaeff,C.; Majoub,M.; Labiad,B.; Villemin. D, Can. J.Chem., 1993, 71, 90Ph-CO1. NBS CH$I;!, MS 481 O°C, PPh32H2. PhCH20H, Py , lh Sucheta,K.; Reddy,G.S.R.;Ravi, D.; -Q&W.fdPhphwco2HVPhPh 7x Tetrahedron98%0 Lett., 1994, 35, 441520%Tic14+ 2 AgC104 Ph+P (ArCO)20 9MS3A Ar = 3,5-trifluoromethylphenyl Shiina,I.; Miyoshi, So.; Miyashita, M.; Mukaiyama,T. Chem. Lett.,HOqCHz)loJL OHPh0 OH5%TiCLz(OTf)z, (ArCO)20 3 TMSCl , CH2C12 (2 mM) reflux (slowadditionover 5 h)Ar = 4-trifluoromethylphenyl Shiina, I.; Mukaiyama,T. Chem. Lett., 1994, 67790% 1994,515A==CJ32ho83% + 10%diolide142Compendium of Organic Synthetic Methods, Vol9C17H31C~Hcat. DMAP , lhSection 108C1f131C%cH~H=CH285% Akiyama, A.; Konda,Y.; Takayanagi,H.; Harigaya,Y. Tetrahedron Mt., 199% 36,NK.; 113Togo. H,; Muraki, T.; Yokovama.M, TetrahedronLett., 1995, 36, 7089Bu-C=C-H, 100°C,5 eq.NEt3 5% Pd(PPh&t, ZnCl;! 84% Liao, H.-Y.; Chew. E.H, J. Org. Chem., 1995, 60, 3711 Furtherexamplesof thereactionRC02H + R’OH + RC02R’areincludedin Section108(Estersfrom AlcoholsandPhenols)andin Section30A (Protection of CarboxylicAcids).SECTION108: ESTERSFROMALCOHOLSAND THIOLSFurtherexamplesof thereactionROH + RCO2R’areincludedin Section107 (Estersfrom Acid Derivatives)andin Section45A (Protectionof Alcoholsand Phenols). 1. BuLi, THF, rt PhmOH;s ph/n/Yco2Et . C02Et 5% Pd(PPh3)4,8h (80:20 E.-Z) 10%PPh3,reflux Star$, I,; Star& I.G.; IWovsky, P. Tetrahedron Lett., 1993, 34, 17980%Section 108143Esters from AlcoholsOH&&j)oa.CL;3.5 Ca(OC1)2,2C02MeAcOH89%32MeOH,darkJd MeCN , rt Nice, L.E.; Shaw, A.W.; Nestor, N.B. TetrahedronLett., 1993, 34, 27411. sOC12, DMF4 C 13H27CH20CH0 2. H20 I.; Garcia, B.; MuAoz, S.; Pedro. J.R,; de la Salud, R. Synlett, 1993, 489CL3H2$H20H Femtidez, tioHKNOflFyl.25Hz0CH2C12,O”C+ rt95%-ON02 95%Olah. G.A,; Wang, Q.; Li, X.; P&ash,G.K.S. Synthesis, 1993, 2071. Cr(CO)9THF,THF, 55OC tw. 81%m.P,; Rahman, S.; Ward, E.L.M. TetrahedronLett., 1994, 35, 3801Pb(OAc), , PhH , CO C3H77OHTsunoi, S .; Byu. I.: Son& Hok40°C) IdN, .I. Am. Chem. Sot., 1994, 116, 5473 NaBrO2, Al203 9 c&cl257%T,; Hirano, M.; Iwasaki, K.; Ishikawa, T. Chem. Z&t., 1994, 5330:1 (2,3-antixyn)Panek.J.S,; Garbaccio,R.M.; Jain,N.F. TetrahedronBuOH ,0.2 M CAN reflux ,75 minLett., 1994, 35, 6453OH Iranpoor.N,; Mothaghineghad, E. Tetrahedron, 1994, 50, 1859158Compendium of Organic Synthetic Methods, Vol. 9Section 124OMe&rk.R.M.;Gac, T.S.; Roof, M.T.S. Tetrahedron Lett., SPDBTO1994,35, 8111SPDBTO 1. Hg(OAc);! , CH2C12 rt , 18h ) Y + +* 2. aq. NaCl 3. Bu$nH, THFSPDBTO# n/OOH+ x/O1) 93% Garavelas, A.; Mavropoulos, I.; Perlmutter.P.; Westman, G. Tetrnhedron Lett., 1995, 36,463(75% Pd(OAc)2, DMSO ,02 23OC, Id OHH‘*623Ronn, M.; BackvaIl, J.-E.; Andersson. P.G, Tetrahedron Lett.,OH1995,BnBr , Cs2CO3, MeCNOH92%OBn80°C Lee. J.C.; Yuk, J.Y.; Cho, S.H. Synth. Commun.,90%,+ H 0 36, 774925, 13671995,1. [email protected] 2. (Cp)zTiMezOiPr 80×80%3. H2, Pd/C Billington, D.C.; Dorey, G. Synth. Commun., 1995,SECTION124: CHOCsHlJETHERS, EPOXIDES FROM ALDEHYDES25,1633AND THIOETHERSBuOH , Pd/C , H2 (40 bar), 100°Calso works with ketones Bethmont, V.; Fache, F.; J,eMaire. M, Tetrahedron Lett.,1995,c8H13 36,4235,OBu95%Section 128Ethers from EstersMe&O-PhCHO Et$iH -s.; 4367159, TMSOTf, CHzC12, -3OOC +O°CMori, H.; Kitano, K.; Yamada, H.; Nishizwa.(tPh-OwM, TetrahedronCH2N2CHOA~(OAI-)~ , -78OC , lhMaruoka, K.; Conception,Ar = 2,5diphenylphenyl A.B .; Yamamoto. H, Synlett, 1994, 521ONTs I Ar’sN Me83%,NaH,THF0 H ‘h,, -5OC, Id PhA Baird, C.P.; Taylor. P.C, J. Chem. Sot. Chem. Comnun., 1995, 893 PhCHOSECTION125:126:ETHERS, EPOXIDES AND THIOETHERS FROM ALKYLS, METHYLENES AND ARYLSETHERS, EPOXIDES FROM AMIDES NO ADDITIONALSECTION127:ETHERS, EPOXIDES FROM AMINES NO ADDITIONALSECTION128:ETHERS, EPOXIDES FROM ESTERS 1. Dibal , -78OCPh’dco2Me63% (70% ee)NO ADDITIONALSECTION99% L&t., 1994, 35,2 . TMSOTf9PyKiyooka. S,; Shirouchi, M.; Kaneko, Y. TetrahedronEXAMPLESAND THIOETHERS EXAMPLESAND THIOETHERS EXAMPLESAND THIOETHERS OSiMe3 pPh TOMe Lett., 1993, 34, 149191%160Compendium of Organic Synthetic Methods, Vol. 9Section 1291.2SmI2, -3OOC + l-t Ph2. [email protected],Mobder.DMAP , TEA CH2C12G.A; McKie, J.A. J. Am. Chem. Sot.,115, 5821PhSH, Pd2(dba)3 , dppb ) THF, IdmocqMeGoux, C.; Lhoste,P.; Sinou.D, Tetrahedron,SECTION1993,ETHERS, ETHERS,129:1994,EPOXIDES EPOXIDESAND THIOETHERS AND THIOETHERSOBna /ow2. H30+Ph44S Ph0 Satoh.T.: Horiguchi,K. Tetrahedron OMeLett., 1995, 36, 44291.2.5 t-BuLi , THF -loo”c2. EtCHO Lett., 1995,-OH36, 8235NaBHgN, Bu3SnCl, AIBN 9hoc90% 0* (x66%1994,38,21651. e’ , Ni (cyclam), DMF , 20°C Mg anode,C fiber cathodeMe,y Ap-Tel.d?Olivero, S.; CIinet, J.C.; Dufiach,E. TetrahedronFROMOBnItoh, A.; Hirose,Y.; Kashiwagi,H.; &&&i. Y, Heterocycles,83%50, 103212 BF3*OEt2,CH2C12 / 0chmSPh12H25Srikrishna.A,; Viswajanani,R. Synlett, 1995, 95(t80%W2H2562%Ethers from KetonesSection 132161Phi ,2% Pd(OAc), ,3 NEt3 6% PPh:, , DMF , 70°CHillers, S.; J&ger. 0, Synlett, 1995, 153SECTION130:ETHERS, EPOXIDES AND THIOETHERS FROM HALIDES AND SULFONATESBER-PhSSPh , MeOH, reflux * CsI-I17-S-Ph Yoon. N.M.; Choi, J.; Ahn, J.H. J. Org. Chem., 1994, 59, 3490 c&317Br 0I96%MeSCHzCl, AlC13 CH2C12 , O°COlah. G.A.; Wang, Q.; Neyer, G. Synthesis, 1994, 276 PhSH, rt SPh Lee, S.B.; Hong,J.-I, Tetrahedrontett., 1995, 36, 8439RelatedMethods:Section123(EthersfromAlcohols).SECTION131:ETHERS, EPOXIDES FROM HYDRIDESAND THIOETHERSPIFA = phenyliodine(III)bis(t.rifluoroacetate) Kita. Y,; Takada,T.; Mihara, S.; Tohma,H. Synlett, 1995, 211SECTION132:ETHERS, EPOXIDES FROM KETONESTsai. Y-M,; Tang,K-H.; Jiaang,W-T. TetrahedronAND THIOETHERSLett., 1993, 34, 130388%162Compendium of Organic Synthetic Methods, Vol. 9PA,,TBAFCapperucci,A.; moceai. A. TetrahedronSection 134A; Ferrara,M.C.; Bonini, B.F.; Mazzanti, G.; Zanti, P.; Ricci,Lett., 1994, 35, 161 0/oAc,Rh2(Ok)4PhF , 10h bPirrun~.M.C,; Lee,Y.R. Tetrahedron69%Lett., 1994, 35, 6231RelatedMethods:Section124(Epoxidesfrom Aldehydes).SECTION133:ETHERS, EPOXIDES FROM NITRILESAND THIOETHERSNO ADDITIONAL EXAMPLESSECTION134:ETHERS, EPOXIDES FROM ALKENES AsymmetricAND THIOETHERSEpoxidation-00Ph -c/N-O, NaOCl +Mn-salenderivative O°C , pH 11.358% (77% ee)Chang,S.; Lee, N.H.; bobsen. mJ. Org. Chem., 1993, 58, 69 39Mn (salen)catalyst , lh 1%H202, O°C, CH2C12 Schwenkreis, T.; Berkessel,A, Tetrahedron Lett., 1993, 34, 4785CO2EtSection 134Ethers from Alkenesthreitol-strapped iodosylbenzeneMn-porphyrin163, CH$I;!A0Ph-, 1,Sdicyclohexylimidazole86% (69% ee, R+) J.P,; Lee, V.J.; Zhang, X.; Ibers, J.A.; Brauman, J.1 J, Am. Chem. Sot., 1993, 115,Collman. 3834chloroperoxidase H202,Bu, acetoneBu9pH 5—-+v78% (96% e-e, 2R3S) Allain, E.J.; Hager, L.P.; Deng, L.; Jacobsen, E.N. J. Am. Chem. Sot., 1993, 115, 4415 Me02%,, Ph Me02CPh,B-OMe0 0t-BuOOH Manoury, E.; Mouloud,H.A.H.; Balavoine, G.G.A, Tetrahedron35% (22% ee , S,S) Asymmetry, 1993, 4, 2339Mn salen catalyst, 02 PhH,rt51% (52% ee) T.; Yamada, T.; Nagata, T.; Imagawa, IS. Chem. Lett., 1993,327Mukaiyama,-0 Ph )=/ PhPh 32 Ph/N-o* cat. Mn salen, O°C , buffered bleach , pH 11.3)7/ Ph69% (93% ee, S,S) Brandes, B.D.; &obssJ. Org. Chem., 1994, 59,4378 cat. Mn(salen) , CH2C12 -phN,,yp (42%ee, lS,2S)Pietikainen.P, TetrahedronLett., 1994, 35, 94149%164Compendium of Organic Synthetic Methods, Vol. 9m I/Section 134 I/ 02Mn salen catalyst, PhIO , O°C72%(98%ee)Sasaki,H.; Irie, R.; w.T, Synlett, 1994, 356 2 PhIO, Mn salencatalystph-PhSasaki,H.;Irie, R.; Hamada,T.; Suzuki,K.; mki. Mn salencatalyst, t-BuCHO PhA“TPhrt T, Tetrahedron,27%(15%ee, lR2R) 1994, 50, 1182702,fl28% (63:37 cis:trans) 80% eefor cis Nagata,T.; Imagawa,K.; Yamada,T.; Mukaiyama,T. Chem. Lett., 1994, 125902, Mn salencomplex, rt NM1 , pivaladehyde, PhF78%(63%ee) T,; Imagawa,IS.; Nagata,T.; Mukaiyama,T. Bull. Chem. Sot. Jpn., 1994, 67, 2248B.Mn (salen)catalyst, Bu4NIO4 imidazole, rt ,3hPh53%(47%ee, lR,ZS (-) ). . ..*Pletlkamen.Tetrahedronc Lett., 1995, 36, 31920%4-Ph-pyridineN-oxide, O°C 5%Mn salencomplex, CH2C12Bran&s, B.D.; Jacobsen. E.N, Tetrahedron Lett., 1995, 36,5123Section 134Ethers from AlkenesPh-1658% Mn salen complex , mcpba , NM0Ph4lCH2C12, -78OC89% (86% ee) Palucki, M.; McCormick, G.J.; Jacobsen. E.N, TetrahedronLett., 1995, 36, 5457chloroperoxidase , KOAc , Hz02 PhantifoamA, aq.acetone,pH 5.2 sodiumcitratePh41111l11189%(49%ee) Dexter, A.F.; Lakner,F.J.; Campbell,R.A.; Hager.L.P,J. Am. Chem. Sot., 1995, 117, 6412a3 NT.;02 , Mn salencatalyst, t-BuCHO70%(64%ee) Imagawa,K.; Yamada,T.; Mukaiyama,T. Bull. Chem. Sot. Jpn., 1995, 68, 1455Non-AsymmetricEpoxidationBIPA , FeCl2,02 70°C, Idmo.BIPA = N,N’-bis(2-(4-imidazoloyl)ethyl)-2,6-pyridinecarboxamide TJ Moriuchi, T.; Mikami, S.; Ikeda, I.; Ohshiro,Y. Tetrahedron Lett., 1993, 34, 1031 cat. [K-lO-montmorilloniteNi(acac)] 0iBuCH0 , CH2C12,rt autoclave,10bar Bouhlel,E.; m. P,; Levart, M.; Montaufier, M-T.; Singh,G.P. Tetrahedron Lett., 1993, 34, 1123 -0. P,; Levart, M. Tetrahedron L&t., 1993, 34, 1127ph*Ph[CoCl&licylaldehyde-L-serinemethylester] w 02,MeCN,rt,25hPunniyamurthy,T.; Bhatia,B.; j,qbal.J, Tetrahedron Lett., 1993, 34,4657‘“TPh 64%67%166Compendium of Organic Synthetic Methods, Vol. 9Fecat.,02,iPrCHO,rtR.W,; Reihs,S.; Hug, M. Tetrahedronalfrank.Section 134* pgF+ e,Lett., 1993,34,96%Ph603310%(NH&H4PV6W&4v6 H20 02, DCE,25OC, 4h 2 eq.iPrCH0 77% Hamamoto,M.; Nakayama,K.; Nishiyama,Y.; Ishii. Y, J. Org. Chem., 1993, 58, 6421Co(mac)2,EtCH(OEt)zC7Hl597%02, MS481.,45OCmat = 3-methyl-2,4-pentanedibne Mukaiyama,T.; Yorozu, M.; Yakai, T.; Yamada,T. Chem. Lett., 1993, 4390I msha.CUE,CH3CH0, CH2C1202,rt, 17h79% S.-I,; Oda,Y.; Naota,T.; Komiya, N. J. Chem. Sot. Chem. Commun., 1993, 139 urea-H202complexfmaleic acid =BUNBu,/f71%Astudillo, L.; GaIindo.A,; Gonzalez,A.G.; Mansilla,H. Heterocycles, 1993, 36, 1075 1. [Mn*‘*(TPP)(Cl)], CHs12 I . O-D.;0 2. imidazole, [email protected],5hTangestaninejad, S. Tetrahedron Lett., 1994, 35,945o= 0, KHSO5 zcH20KH2C12(pH 11) 18-crown-6,5”C w. .(9 M,; Ito, S.; Tsutsumi,N.; M&&J,&TetrahedronMt.,91) 80%1994, 35, 1577Section167Ethers from AlkenesAgOAc/bipy/anode ACN (0.1 M LiCLO4) H20Kandzia,C.; Steckhan. Tetrahedron-%diPrCH0, Fe(AAEMA)3 p02rt, 10h(-)=, AAEMA =87%Mt., 1994, 35, 369500Mastrorilli, P.; Nobile, C.F, TetrahedronLett., 1994,PhzP-‘-PPh, II35, 4193 0II87%* k=Ph -LA,&;Ph H202 Delair, P.; Blass,B.E. Tetrahedron Lett., 1994,35, 8123 S II1.EtOlPEt0SBn2. TBAF.3 H20 wG.;82%Mecichetti, S.; Neri, S.; Skowr0nska.A. Synlett, 1994, 267 NaOCl ,4-methylpyridinehJPJ88%porphyrincatalyst/Mn ; Pereira,M.M.; Serra,AC.; Johns~&pe. R.A.W; Nunes,M.L.P.G. J. Chem. Sot., Perkin Trans. I., 1994, 2053YO~OZU. K;Takai,C7H1502 (1 atrn),2% Co(acac)z EtCH(OEt)2,45OC, 1Oh> 48%0 T.; Yamada,T.; Mukaiyama,T. Bull. Chem. Sot. Jpn., 1994,67, 2195Compendium of Organic Synthetic Methods, Vol. 9168Section 134Oxone, 0°C , Bu4NHS04 tIOBnacetone , CH-$&OBn, buffer 99%Denmark.S.E,; Forbes,D.C.; Hays,D.S.; DePue,J.S.; Wilde, R.G. J. Org. Chem., 1391 M 0 ‘-x Fg 61995,60,, MeCN, O°C> 15min Me Yang. DJ Wong, M.-K.; Yip, Y.-C. J. Org. Chem.,1995,60, 3887CO2H I 2 US.;0-Jhv , methyleneblue PhH , Hz0/ Thanulingam,T.L.; Rajesh,C.S.; George,M.V. TetrahedronChen,Y.; Beymond.J.-L, Tetrahedron Lett.,1995,Lett., 1995,36, 133736,4015t-B&OH, Ti(OiPr)d, SiO2 w rt, Id Fraile, J.M.; Garcia,J.I.; Mayoral. J,A,; deMhorval,L.C.; Rachdi,F. J. Chem. Sot. Chem.Commun., 1995,539PhIO, NaOCl, Mn salencatalyst t Rasmussen, KG.; Thomsen,D.S.; mn. 2009w.92%K.& J. Chem. Sot., Perkin Trans. l., 1995,Section 135Ethers from Misc.t-B&OH,169OHMeOHCrS-2- molecular sieve85%. Joseph, R.; Sasidharan, M.; Kumar. R… Sud& . A… Ravmdmnathu Commun.,1995,134lFormationBosman,C.; DA-ale.of Other EthersPhSeSePh , CAN IJ. Chem. Sot. Chem.MeOH ,30 min-c,A; Resta,S.; Troeolo. C, TetrahedronSePh 93% “%, OMeLett., 1994, 35, 652597%Marshall. J.A,; Sehon,C.A. J. Org. Chem., 1995, 60, 5966 REVIEW:“RationalDesignof Manganese-Salen EpoxidationCatalyts;PreliminaryResults,”Hosoya, IV.; Hatayama,A.; Irie, R.; Sasaki,H.; Katsuki.T, Tetrahedron, 1994, 50, 4311SECTION135:ETHERS, EPOXIDES AND THIOETHERS FROM MISCELLANEOUS COMPOUNDS PhSSPh, SbC15,DCE OMePhS-(=)-OMereflux ,3h 76% Mukaiyama, T.; Suzuki, K. Chem. Lett., 1993, 1 LiAlH4, Tic14 PhSOzMe w 93% PhSMe Akgiin, E.; Mahmoud,K.; Mathis. C.% J. Chem. Sot. Chem. Commun., 1994, 761170Compendium of Organic Synthetic Methods, Vol. 9r’u S[SiO2/SOCl2] 10min‘rsy73%Mohanazadeh. F,; Momeni, A.R.; Ranjbar,Y. Tetrahedron Lett., 0 IISection 1351994,35,6127CpzTiC12,Sm, THF , rt wPh/‘Me Zhann. Y,; Yu, Y.; Bao, W. Synth. Commun., 0 IIPh”‘ Ph Wang, J.Q.; Zhanrr, Y.M,Synth.1995,77-88%25, 1825TiC14,Sm, THF , rt ,30 min Commun., 1995,Ph/‘Me25, 3545Ph”,PhCompendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)Section 138CHAPTER10PREPARATION SULFONATESSECTION 136:171Halides fkomAlcoholsOF HALIDESANDHALIDES AND SULFONATES FROM ALKYNES NO ADDITIONAL EXAMPLESSECTION 137:HALIDES AND SULFONATES FROM ACID DERIVATIVES PhIO , NBS , MeCN , 60°C *Ph-C02HPh+Br 73%Graven, A.; aSECTION 138:(96:6 cis:trans)K& Dahl, S.; Stanczdc,A. J. Org. Chem., 1994, 59, 3543HALIDES AND SULFONATES FROM ALCOHOLS AND THIOLSPPh3, (C13COCh0 w PhCH2Cl PhCHzOH Rivero, I.A.; SomanatXlan.; Hellberg, L.H. Synth. Commun., 1993, 23, 7 1195%BBr~,CH$ld)°Cw < .Pelletier, J.D.; poiuTetrahedron L&t., 1994, 35, 1051TMSCl , DMSO wh7-4H&y&D.C, J. Org. Chem., 1995, 60, 2638c$H 174195%172Compendiumof Organic Synthetic Methods, Vol. 9o-OH12, pet ether, reflux , 1.5hSection 14242%Joseph,R.; Pallan, P.S.; Sudalai, A.; bvindranathm. T, Tetrahedron Left., 1995, 36, 609 Me$iCl , BiC13 OHrt ,90 min f Labrouihere, M.; Le Roux, C.; Oussaid,A.; Gaspard-Boughmane,H.; Dubuquant. Bull. Sot.Chim. Fr., 1995, 132, 522REVIEWS:“An Alternative Synthesisof Aryl and Heteroaryl Bromidesfrom Activated Hydroxy Compounds,” IQ&&&y. A.&; Li, J.; Stevens, C.V.; Ager, D.J. Org. Prep. Proceed. int., 1994, 26,439SECTION 139:HALIDES AND SULFONATES FROM ALDEHYDES NO ADDITIONAL EXAMPLESSECTION 140:HALIDES AND SULFONATES FROM ALKYLS, METHYLENES AND ARYLSFor the conversionR-H + R-Halogen,seeSection 146 (Halides from Hydrides). 2 eq. VO(OEt)CZ2,N2 MeCN , O°C+ rt Ph~si~3PhwC16oo/ 0Fujii, T.; Hirao. T,: Ohshiro. Y, Tetrahedron Lett., 1993, 34, 5601SECTION 141: HALIDES AND SULFONATES FROM AMIDES NO ADDITIONAL EXAMPLESSECTION 142: HALIDES AND SULFONATES FROM AMINES 1. TolSO~l 2. base PheNH23.NBS,THF,hvPh-Br86% Collazo. J&; Guziec Jr., F.S.; Hu, W.-X.; Pankayatselvan,R. Tetrahedron Lett., 1994, 35, 7911Section 146Halidesfrom Hydrides173SECTION 143: HALIDES AND SULFONATES FROM ESTERS NO ADDITIONAL EXAMPLESSECTION 144:HALIDES AND SULFONATES FROM ETHERS, EPOXIDES AND THIOETHERS NO ADDITIONAL EXAMPLESSECTION 145:HALIDES AND SULFONATES FROM HALIDES AND SULFONATES n-CgH17I, KF , GUICICF~02MeC&I&F3Cd12, HMPA , 120°C, 8hChen. Q-Y,; Duan, J.-X. Tetrahedron Lett., 1993, 34, 4241SECTION 146:+ CO2 + MeCl77%HALIDES AND SULFONATES FROM HYDRIDESa-Halogenationsof aldehydes,ketonesand acidsare found in Sections338 (Halide-Aldehyde),369 (Halide-Ketone),359 (Halide-Esters)and 319 (HalideAcids).BrF3, Br2 , O*CBr Rozen, S,; Lerman, 0. J. Org. Chem., 1993, 58, 239OMeBP-(=)-OMeCH2C12,MeOH 90% Bisawa. SC,; Rao, R. Synth. Commun., 1993, 23, 779(tPyH Br3, THF NJ32–I/&eves.W.P,; King II, R.M. Synth. Commun., 1993, 23, 85587% (19:68 o:p)Section 147Compendium of Organic Synthetic Methods, Vol. 9174NBS/cat. HZSM-5 OMecc4XeF2, MeCN ,25OC, 6h /CHOFQCHOI H Wang, J.; Scott. AJ, Tetrahedron Lett., 1994, 35, 3679’c’ -/I HNH4VO3, H202, KBr 2 phase (H201CHCl3) ,25OC35%/- r *50%Bf/ 9 9 0Conte, V.; Di Furia. F,; Moro, S, Tetrahedron Lett., 1994, 35, 7429 I2Qm03)2CH2C1252%20°C , 14hBachki, A.; Foubelo, F.; Yus, M, Tetrahedron, 1994, SO, 5139(t (tHgO-120, CHg12 OBn */&jto.$=)-OBn87%L; Hatakeyama, T.; Takeo, M.; Suginome, H. Synthesis, 1995, 1273 NBS , AcOH , ultrasound, 6h OMe * ..~-(=)-OMe/92%Paul, V.; Sudalai, A.; Daniel, T.; Srinivasan. K,V, Synth. Commun., 1995, 25, 2401SECTION 147:HALIDES AND SULFONATES FROM KETONES CF2Br2,Zt-tILu. C.-M,; Qing, F.-L.; Shen, C.-X. J. Chem. Sot., Perkin Trans. l., 1993, 335Section 150Halides from Misc.175SECTION 148: HALIDES AND SULFONATES FROM NITRILES NO ADDITIONAL EXAMPLESSECTION 149:HALIDES AND SULFONATES FROM ALKENESFor halocyclopropanations,seeSection 74E (Alkyls from Alkenes). HCl , SiO2 Cl 62% 0 Kn]DD. P.J,; Daus, K.A.; Tubergen, M.W.; Kepler, K.D.; Wilson, V.P.; Craig, S.L.; Baillargeon, M.M.; Breton, G.W. J. Am. Chem. Sot., 1993, 115, 30710Ima.KHF2 , SiF4, rt79%M; Shibakami, M.; Kurosawa, S.; Arimura, T.; Sekiya. pb,J. Chem. Sot. Chem.Commun., 1995, 1891SECTION 150:Ph-N=N-NHALIDES AND SULFONATES FROM MISCELLANEOUS COMPOUNDS12, CH212,80°C ,4hPh-I>98%Wu, 2.; Jvfoare; J& Tetrahedron Lett., 1994, 35, 5539Fz,Iz,MeCN,rt +db ‘Chambers.;-;I’L /I’52% Atherton, M. .I. Chem. Sot. Chem. Commun., 1995, 177SOC12,DMF , 100°C 81% C~H25S03Na w325Cl Carlsen, P.H.J.; Rist, 0.; Lund, T.; Helland, I. Acta Chem. Stand. B., 1995, 49, 701Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)176Section 153Compendium of Organic Synthetic Methods, Vol. 9CHAPTER11PREPARATIONOFHYDRIDESThis chapter lists hydrogenolysis and related reactions by which functional groups are replaced by hydrogen: e.g. RCH2X + RCH2-H or R-H.SECTION151: HYDRIDESFROMALKYNESNO ADDITIONALSECTION152: HYDRIDESFROMEXAMPLESACID DERIVATIVESThis section lists examples of decarboxylations (RC02H + R-H) and related reactions. NO ADDITIONALSECTION153: HYDRIDESFROMEXAMPLESALCOHOLSAND THIOLSThis section lists examples of the hydrogenolysis of alcohols and phenols (ROH + R-H). 1. (Bu3Sn)p, To1 , reflux , Id (90%)QH2hoH2.2 eq. EtNCO3. Et$iH , PhH , 140°C 0.05M , benzoyl peroxide (70%) Nishivama. K,; Oba, M.; Ishimi, M.; Sugawara, T.; Ueno, R. TetrahedronPh-OH1. [PPh3/rf20] , CH2C12 2. NaBH4, rt3.1NHCl Hendrickson. JB,; Singer, M.; Hussonin, Md.S. J. Org. Chem.,Wustrow. D.J%;Smith III, W.J.; Wise, L.D. Tetrahedron* 1993,ktt.,1993,Phn 87% 58, 6913L&t., 1994, 35, 6134, 3745Section 157Hydrides from AminesH u;Cusack, K.P.; Kwochka,H W.R. Tetrahedron Lett., 1994, 35, 1477PPh3, Et.$IBr , MeCNCH3-(CHd9-QH177e’C&—W2)g—H94% Maeda, H.; Maki, T.; Eguchi, K.; Koide, T.; Qhmori. H, Tetrahedron Lett., 1994, 35,4129 CBH17-OH1. MeCON=C=Sw C8Hl~ 2. Ph$iH , AIBN , 80°C, 10 min48~83%Oba, M.; Nishivama, K, Synthesis, 1994, 624 Also via: Section 160 (Halides and Sulfonates).SECTION154: HYDRIDESFROMALDEHYDESFor the conversion RCHO + R-Me, etc., see Section 64 (AIkyls from Aldehydes). NO ADDITIONALSECTION155:HYDRIDES FROM AND ARYLS NO ADDITIONALSECTION156: HYDRIDESFROMEXAMPLESALKYLS,METHYLENESEXAMPLESAMIDESNO ADDITIONAL EXAMPLESSECTION157: HYDRIDESFROMAMINESThis section lists examples of the conversion RNH2 (or R2NH) -+ R-H.e- , TI-IF/HzO ,60% HNO3 67%Tpfii. S,; Okumoto, H.; Satoh, H.; Minoshima, T.; Kurozumi, S. SynZett, 1995, 439178Compendium of Organic Synthetic Methods, Vol. 9SECTION158: HYDRIDESFROMSection 158ESTERSThis section lists examples of the reactions RC02R’ + R-H and RCO2R’ + R’H, HO \+ UT.;Pd(acac)z , PBu3 , rt PhH ,3h(alkyne:allene = 99: 1)CSh7Matsumoto, T.; Kawada, M.; Tsuii. J, Tetrahedron$=J$SMeII other initiators34, 2161hv (tungsten lamp) Bu$nH , 0°Cl-BflqSi()iLett., 1993,f-l34,2733u-o’Nywere .also usedBarton, D.H.R.; parekh. S&; Tse, C.-L. TetrahedronLett., 1993,SMe 5 eq. PhSiH3, AIBNtoluene , reflux , lh Barton, D.H.R.; Jang, 0.0.; Jaszverenyi, J.Cs. Tetrahedron,43quant.1993, 49, 2793, 7193dcoxygenated cyclohexane AIBN , 80°C 99% Gimisis, T.; Ballestri, M.; Ferrer-i, C.; Chatgilaloglu. C,; Boukherroub, R.; Manuel, G. TetrahedronLett., 1995, 36, 3897Section 160PhACTBAFex Hz0 , NM0 , THF , rt 1,3-propanedithiol PhPh Phw 00 Uelo. M4; Okamura, A.; Yamaguchi, J. TetrahedronSECTION179Hydrides from HalidesHYDRIDES FROM THIOETHERS159:99%Lett., 1995, 36, 7467ETHERS,This section lists examples of the reaction R-O-R’ +Me Hamel. P,; Zajac, N.; Atkinson, J.G.; Girard, Y. TetrahedronEPOXIDESANDR-H.Lett., 1993, 34, 20595 eq. Ni2B , MeOH-THF tC 11H23-S-Ph2 NiBr2+6 NaBH4__I_)Ni2B90%c 1 lH24Back. T.G,; Baron, D.L.; Yang, K. J. Org. Chem., 1993, 58, 2407DMN* , ascorbic acid , iPr0H hv,3hSePh &Q&Y.DMN*= photoactivateda=’1,5-dimethoxynaphthalene85% Cr,; Rao, K.S.S.P.; Sekhar, B.B.V.S. J. Chem. Sot. Chem. Commun., 1993, 1636SECTION160:HYDRIDESFROMHALIDESAND SULFONATESThis section lists the reductions of halides and sulfonates, R-X + R-H.57% HI, 25OC, 15 min98%Wll WllBr Penso. M,; Mottadelli,S.; Albanese, D. Synth. Commun., 1993, 23, 1385180Compendiumof Organic Synthetic Methods, Vol. 9Section 160Br MeLi,THF , -105OC52%b-Br% Grandjean, D.; pale. P, TetrahedronL&t., 1993, 34, 1155M+ B:i,-,:::“;HcHLH OCH2CH2CH2Bran aryltranslocation24% Lee. EJ Lee, C.; Tae, J.S.; Whang, H.S.; Li, KS. TetrahedronC3H761% Lett., 1993, 34, 2343OH ClClNaBHz(OCH2CH20MehClNiCl2, MeOCHzCHzOH THF ,68OC, 2hCl Tabaei, S.H.; Pittman Jr.. CU, Tetrahedron-4Lett., 1993, 34, 3263HC02H , Pd/C , toluene H20, NazCO, , 90°C Cl Cl Barren. J-P,; Baghel, S.S.; McCloskey,quant. P.J. Synth. Commun., 1993, 23, 1601PVP-PdC12, H2, 65OC ambient pressure , EtOH , NaOH PVP-PdC12 = palladium anchored on poly(N-vinyl-2pyrrolidinone) Zhang, Y.; Liao. S,; Xu, Y. Tetrahedron Lett., 1994, 35, 45990 quant.Section 162cti181Hydrides from Ketonesborohydride exchange resin , rt ,3h 0.1 Ni(OAc), , MeOH17—BfYoon. N.m, Lee, H.J.; Ahn, J.H.; Choi, J. J. Org. Chem.,&I&I.U,; Sanna, K.D. TetrahedronSECTION161: HYDRIDESLett., 1994,FROM35,CSH 17-H quant. 59, 46871994,7861HYDRIDESNO ADDITIONAL EXAMPLESSECTION162: HYDRIDESFROMKETONESThis section lists examples of the reaction R2C-(C=O)R Et3SiH , BF3mOEt2, CHg12+ R2C-H.ph-Ph mu.Ph 92%L Synth. Commun., 1994, 24, 1999NaBHgN, BFpOEt2, THF *rt, 12h‘(+(=)–c130–(=)- 94%Srikrishna. A,; Sattigeri, J.A.; Viswajanani, R.; Yelamaggad, C.V. Synlett,1995,93OzC02MeOH1. ClC02Me2, NaBH3OHI -OH 94×76%. ltw. 36,5335D,; Doecke, C.W.! Hay, L.A.; Koenig, T.M.; Wirth, D.D. TetrahedronLett., 199%182CompendiumNHc~Meof Organic Synthetic Methods, Vol. 91. Me$iClSection 165NHCO2Me, NEt32. Et$iH , Tic13 PhAA b Ph &CO,H ma–I Yato, M.; Homma, K.; Jshida. A, Heterocycles, 1995, 41, 17NaCNBH3, THF BFyOEt;!, rt ,30 min 4g5%Me0 shna. A,; Viswajanani,SECTION.. 2) 85% (3 R.; Sattigeri, J.A.; Yelamaggad, C.V. Tetrahedron163: HYDRIDESFROMSmI2, THF-HMPA1995,36,NITRILESThis section lists examples of the reaction, R-C=N + isonitriles (R-N&). CNtiff.,R-H (includes reactions ofPh, 0°CCN 97%CN Ph 3 Hong, W.S.; Cho. Y.S,; Koh, H.Y. Tetrahedron Lett., 1995,SECTION164: HYDRIDESFROMALKENESNO ADDITIONALSECTION165: HYDRIDESFROMH 36, 7661EXAMPLESMISCELLANEOUSCOMPOUNDSMg , EtOH , cat. HgCl2 PrtLee, G.H.; Choi, E.B.; Lee, E.: Pak. C& Tetrahedron98% Lett., 1993, 34, 4541Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)Section 166Ketones from AlkynesCHAPTER18312PREPARATIONOF KETONESSECTION 166: KETONES FROM ALKYNESCha. JS,; Min, S.J.; Kim, J.M.; Kwon, 0.0. Tetrahedron Lett., 1993, 34, 5113. Tekeuchl.,78% Yasue, H. J. Org. Chem., 1993, 58, 5386MeCN , 760°C, 4h OMe CO)sCr+ Me(11:l ,33%) Kim, O.K.; 1;vulff. W.D%; Jiang, W.; Ball, R.G. J. Org. Chem., 1993, 58, 5572 0Ph 1.10% c02(c0)8,DME2.20% P(OPh)3 , refluxIwasawa, N.; Matsuo, T. Chem. Lett., 1993, 997Compendiumof Organic Synthetic Methods, Vol. 9Section 1671. BrzBH*SMez 2. propylene glycol BrBu* 3. CH2=CHCH2MgCl, THF , -78OC 4. HMPT , THF , 50°C, HMPA 5. oxidation Brown. H.r; Soundararajan,R. Tetrahedron Lett., 1994, 35,6963Bu* 95%MeReO3, H202, tOH PhPhPhPh 4f 080%Zhu, 2.; EsPenson.J.ltI, J. Org. Chem., 1995, 60, 7728SECTION 167: KETONES FROM ACID DERIVATIVESPhpAc1 TiCl&Zn ,3% HClp)$+;+p;)=(;69%24%Shi, D.; Chen, J.; Chai, W.; men. W,; Kao, T. Tetrahedron Lett., 1993, 34, 2963 1. (C6h3)2Zn2. CuCN.2 LiCl98%Langer, F.; Waas,J.; -eI. ClP, Tetrahedron Lett., 1993, 34, 5261 e’ , [email protected], rtPTPh80%meCN 0 0 st. J.-C,; Pereira-Martins, E.; Troupel, M.; Perichon, J. Tetrahedron Lett., 1993, 34, 7571 1. (Me2N=CHCl)Cl, Py MeCN/THF 2 5eq NaN3 O°C * Pa 3:oYG rt ’ Affandi, H.; Bayguen, A.V.; J&&&W, Tetrahedron Lett., 1994, 35, 2729 pt(/co2H90% N3185Ketonesfrom AcidsSection 167Me0 CgHllCOOH , (PhCO)20, Id 20% (Sic14+ 3 AgC104) CH2C12,rt Me0 T, BUZZ.Chem. Sot. Jpn., 1993, 66, 3729Kitagawa, H.; m&Z&&K.;PhBU’n*SnBu3 ClPhPd(PPh& , dioxane 100°C, 30 hPh+ 50%Echavarren. A.M,; Perez,M.; CastaiIo, A.M.; Cuerva, J.M. J. Org. Chem., 1994, 59, 41791. (Ph0)2PON3, NEt3 dioxane , reflux 2.2 M HCl?mHW 0 w;61% (2.83 cis:trans) Cowell, J.K.; Harris, L.J. Tetrahedron Lett., 1994, 35, 38830I 0t-BuCl/Li/ ultrasound Liofl, THF76% Aurell, M.J.; Einhom, C.; Einhom, J.; Luche. J.L. J. Org. Chem., 1995, 60, 8PhC02LiiPrC1, Li , THF , ultrasound, rt63% ’ Aurell, M.J.; Danhui, Y.; Einhom, J.; Einhom, C.; Luche, J.L, Synlett, 1995, 459186Compendiumof Organic Synthetic Methods, Vol. 9OHNaI04, MeOH, TEBAPhxCO2H Kore, A.R.; Sagar,A.D.; &&&&. 092% * DB-18-c6 Ph-L Ph M.m Org. Prep. Proceed. Int., 1995, 27, 373Ph* ClHan, Y.; Fang, L.; Tao, W.-T.; m.Cl[PhJGaBuJLi, THF-hexane , 0°C4fClSection 16882%PhY.-Z4 Tetrahedron Lett., 1995, 36, 1287PhPhMgBr , CuBr , LiBr , THF , 0°CPh75%Babudri, F.; Fiandanese,V.; Marchese.G; Punzi, A. Tetrahedron Lett., 1995, 36, 7305m.EtMgBr , Ni(dppe)Clz 70%Ph * Cl PhL C,; Aronica, L.A.; Lardicci, L. Tetrahedron Lett., 1995, 36,9185SECTION 168: KETONES FROM ALCOHOLS AND THIOLS 0.2% his-Ru catalyst, THF 65OC 99% w BackvaIl, J.-E.; Andreasson,U. Tetrahedron Lea., 1993, 34, 5459 1. t-B&OH, H+ *Ph2. DBU80x58% Antonioletti, R.; Arista, L.; Bonadies, F.; Locati, L.; 8cett.t-i.A, Tetrahedron Lett., 1993, 34, 7089 !1. RuC13.nHz0 , Co(OAch.4 Hz0 2. ;i;k-;,&Ho, 2o”c =c )Murahashl.. S.-L; Naota, T.; Hirai, N. J. Org. Chem., 1993, 58, 731889%187Ketonesfrom AlcoholsSection 1680.05 Cr03 ,3 eq. 70% t-BuOOH96%CH2C12, rtPh Muzaft.1; Ajjou, ANA. Synthesis, 1993, 785 01. Co(Imd)2 , EtOAc Ph Ph P LH 2. imidazole , CH2C12 0 68% S.-L; Park, D.-C.; Rho, H.-S.; Han, S.-M. Synth. Commun., 1993, 23, 2219OH PDC , Celite , CH2C1225OC, Id55%Bijoy, P.; Subba Rao. G.S.R,Synth. Commun., 1993, 23, 2701 Cal37PhI=O ,;(NO&, DCEz&l37OH aldehydescan also be formed quant. Yokoo, T.; Matsumoto, K.; Oshima. K.: UtimoK. Chem. Lett., 1993, 571(tV205 , Z1-02, toluene 0OH llO°C, 6h-o=aldehydescan also be formed Nakamura, H.; Matsuhashi, H.; Arata, K. Chem. L&t., 1993, 749-Q588%5% CoSANSE, MeCN 60070°C, 02, 17h –Q+CoSANSE = ~is(salicylidene-N-(methyl-3-hydroxypropionate))] Co Punniyamurthy, T.; Iabsl. Tetrahedron Lett., 1994, 35, 400772%188Compendium of Organic Synthetic Methods, Vol. 9Phi ,3% Pd(OAc)2, DMFSection 168Ph+O3 eq. KOAc , 80°C, 3d40%Larock. RC,; Yum, E.K.; Yang, H. Tetrahedron, 1994, 50, 3059 02OH(t79%CoSANSE * o= CoSANSE = chiral cobalt catalyst IQ&a, S.J.S.; Punniyamurthy, T.; Iqbal. J, Tetrahedron Lett., 1994, 35,48479 J+ zt-B&OH, EhNOH , rt [OsO4] , aq. t-BuOH ,fiHOi k1 OH Beck, C.; Seifert. & Tetrahedron Lett., 1994, 35, 7221 0.5% Ru complex ,20% Co complex 0.5 02 , toluene , 1OOOC,36h 87% 2,5-dit-butyl-1,4-benzoquinone0 OH Wang, G.-Z.; Andreasson,U.; Backvall. J.-E, J. Chem. Sot. Chem. Commun., 1994, 1037 cat. PdC12, cat. Adogen 464 9.3h, Nag03 , DCE , refluxA&Mohand,t-B.=-(-}=Oalso for primary alcohol + aldehydes S.; Henin, F.; Muz . J, Tetrahedron Lett., 1995, 36, 2473“;;;;t”,;OAct-B+(-)=0 96%Murahashi. S-I,; Naota, T.; Oda, Y.; Hirai, N. Synlett, 1995, 733189Ketonesfrom AldehydesSection 169OH Co(acac)3,02, MeCN ,75’C93% O Iwahama, T.; Sakaguchi,S.; Nishiyama, Y.; Ishii. Y, Tetrahedron Lett., 1995, 36, 69236DBacillus stearothemophilus‘4 %heptane640 49% 100%ee (lS,SR) Fantin, G.; Fogagnolo, M.; Giovannini, P.P.; Medici. A; Pedrini, P.; Poli, S. Tetrahedron Lett., 1995, 36, 441 OH‘OHcat. CoC12(PPh& , t-BuOOH /93%DCE , heat, 4.5hPhaldehydescan also be formed Dyer. &; Varghese, J.P. Synth. Commun., 1995, 25, 2261 He’ , RuO2, aq. MeCN , Bu,$JOH89%Bu$JBr Ph Torii, S.; Yoshida, A. Chem. Lett., 1995, 369 RelatedMethods: Section48 (Aldehydesfrom Alcohols and Phenols).SECTION 169: KETONES FROM ALDEHYDES0.05 Rh(R-BINAP)ClOd CH2C12,rt ,30 min(397) 81% (>99%ee3S,4S)Wu, X.-M.; Funakoshi, K.; Sakai. K, Tetrahedron Lett., 1993, 34, 5927190Compendium of Organic Synthetic Methods, Vol. 9Section 16971% Punniyamurthy, T.; Kalra, S.J.S.; Qbal. J, Tetrahedron Lett., 1994, 35, 2959PhCHO1. t-BuMe$iCBrzLi 2. set-BuLi, -78OC + rt3. PhCHO 4. HMPA Shinokubo, H.; Oshima. K.: IJtimotuPhkPh5g%Tetrahedron Lett., 1994, 35, 374159% (78% ee , S) Barnhart, R.W.; Wang, X.; Noheda, P.; Bergens, S.H.; Whelan, J.; Bosnich.B,. Am. Chem. sot., 1994, 116, 1821 Me$iCBr3PhCHO, CrBq/LiAlHqTHF , 60°Cmn.D.M.; Comma, P.J. Synlett, 1994, 663PhCHO CH(OEt)3, H+ , THFKatritzkv.2. BuLi, THF , -78OC 94% 3. EtBr 4. H+ A.R,; Lang, H.; Wang, 2.; Zhang, 2.; Song, H. J. Org. Chem., 1995, 60, 7619 C&I $xCpCl,20% ZnBr2PhCHOPhCHO *THF ,3h ,25OC Zheng, B.; Sreb&M, J. Org. Chem., 1995, 60, 3278Section 171Ketones from AmidesSECTION 170:191KETONES FROM ALKYLS, METHYLENES AND ARYLSThis section lists examples of the reaction, R-CH2-R’ -3 R(C=O)-R’. 5% CoSANSE , MeCN Ph-Phcat. 2-oxocyclopentene carboxylate 60°C, 15h, O2 CoSANSE = ~is(salicylidene-N-(methyl-3-hydroxypropionate))] Co Punniyamurthy, T.; IabaI. J, Tetrahedron Lett., 1994, 35, 4003t’h69%OMe [email protected], Me$YBF3 CH2C12, -78OC+ rt 76%Kiselyov, A.S.; m.R.G, Tetrahedron Lett., 1995, 36, 4005SECTION 171: KETONES FROM AMIDESMeN I OMeOMe I N Me0 1.2 eq. PhLi Ph +2 . H+Ph 4f75% OSibi. M.P,; Marvin, M.; Sharma, R. J. Org. Chem., 1995, 60, 5016 1.2.2 BuLi , -78OC cN-(,Pht 2. AcOH 3. K,C03,65°C,.jiph82% Brandange, S.; Holmgren, E.; Leijonmarck, H.; Rodriguez, B. Actu Chem. &and. B., 1995, 49, 922 GN-1.2 eq. PhLi tC02Et 2. H30+Ph Prakash, G.K.S.; York, C.; Liao, Q.; Kotian, K.; Qlah. G.A, Heterocycles, 1995, 40, 7995%192Compendiumof Organic Synthetic Methods, Vol. 9Section 1722 eq. EtAIC12, rt , 12h Ph Ph7N I56%PhCH2Qso2Iwama, T. Tetrahedron Lett., 1995, 36, 245-T.;PhMgBrPhK68% Ph. Kashlma. CJ Kita, I.; Takahashi, IS.; Hosomi, A. J. Heterocyclic Chem., 1995, 32, 25 REVIEW:“Chemistry of N-Methoxy N-Methyl Amides. Applications in Synthesis.A Review,” S M.P. Org. Prep. Proceed. Int., 1993, 25, 5SECTION 172: KETONES FROM AMINES 1. “X” 2. H30+3 = H40% X = octane,230°C ,2h X = t-BuOK./BuLi/THF/-50°C ,2h 73% Sprules, T.J.; Galpin, J.D.; Macdonald, D, Tetrahedron Lett., 1993, 34, [email protected] W04 9ether 25OC, lhHarris, C.E.; Lee, L.Y.; Dorr, H.; Singaram. B, Tetrahedron Lett., 1995, 36, 292175%Section 174Ketonesfrom Ethers193/OH o= % )=c7% 86% Gao, J.; Hu, M-Y.; Chen, J-x.; Yuan, S.; Chen, W-x Tetrahedron L&t., 1993, 34, 161786%PaLett., 1993, 34, 3951Section 177Ketonesfrom KetonesTick, CH&19992%lIllIIIIIISi(i~)3-78OC + -2OOC& Kniilker. H.-J; Graf, R. Tetrahedron Let?., 1993, 34,4765(5: 1 anti:syn)98~72%pandey. G,; Krishna, A.; Girija, K.; Karthikeyan, M. Tetrahedron Let?., 1993, 34,663l 1. LiN(TMS)z A/q/:-.:;:,.,,4h+ + 95%Reetz.;Haning, H. Tetrahedron Let?., 1993, 34, 7395Cossy. J,; Furet, N. Tetrahedron Let?., 1993, 34, 8107kEi:%ir?-t, 18h ) &J~.I+ 56~~~lohexmoJ&&s. R&; Taylor, S.R. .I. Org. Chem., 1993, 58, 4469Cahlez. G,; Figadbe, B.; Cl&y, P. Tetrahedron Let?., 1994, 35, 3065Section 177Compendiumof Organic Synthetic Methods, Vol. 9200,,,,\I”’TMSCF$&Ag, Me1 -CH2C12,-78OC+ rt..(6 1 P, Tetrahedron Lett., 1994; 35, 367Angers, P.; we.rc 1)Chen, L.; Gill, G.B.; Pattenden.G, Tetrahedron Lett., 1994, 35, 2593 1. MeLi 2. MnC12 Ph3. PhCH2Br ; Chau, K.; Cl&y, P. Tetrahedron Lett., 1994, 35, 3069 0 0BuAMeCHN2 , Me3Al ,O”C CH2C12, lhBuMaruoka, K.; Conception, A.B.; -to./I & #55%Me I& J. Org. Chem., 1994, 59,47252.5 eq. BuySnH , AIBN *Cl0TBu Bu K,8h slow additionq 0 Dowd. PJ Zhang, W.; Mahmood, K. Tetrahedron Lett., 1994, 35, 556357%78%201Ketonesfrom KetonesSection 177SC-1 , Ni2B , H2 (1 atm) 0*o=OQ-OH(>99: B, Tetrahedron Lett., 1994, 35, 5595BeIisle, C.M.; Young, Y.M.; SSiMe3PhPhPh1) >99%PhYb,THF,40°C,2hCHPh;!‘r(PhPhOH 68% 29% Taninuchi. Y,; Nagafuji, A.; Makioka, Y.; Takaki. K.: Fujiwara. Y, Tetrahedron Lett., 1994, 35, 6897 0hv’NEt348%Kirschberg, T.; [email protected] J, Tetrahedron Lett., 1994, 35, 7217 Ph Rh2(O$R*)4, CHgl2, -2OOC,2h 0 PhN264%(77% ee , S) Watanabe,N.; Ohtake, Y.; &phimoto. S,; Shiro, M.; Ikegami, S. Tetrahedron L&t., 1995, 36, 1491PhPhCHOPh *S 2277Ph84%cat. TMSOTf , rt , CH#2,5h 0 SE; Awachat, M.M.; Kelkar, S.V. Tetrahedron L&t., 1995, 36,Section 179Compendium of Organic Synthetic Methods, Vol. 9202C&12, SmI2, TI-F ,5h61% -s.;Tsuchimoto, T. Tetrahedron Lett., 1995, 36, 5937 Bu$nCl – NaBH3CN, AIBN SO;?Pht-BuOH , heat86% Giovannini, R.; Petrini. M,Synlett, 1995, 973 REVIEW: “Organotin Enolates in Organic Synthesis. A Review,” Shibata. I,; Baba, A. Org. Prep. Proceed. Int., 1994, 26, 123 Related Methods: Section 49 (Aldehydes from Aldehydes).SECTION 178: KETONES FROM NITRILES NO ADDITIONALEXAMPLESSECTION 179: KETONES FROM ALKENES1,4-dimethoxybenzene(sensitizer) hv , MeCN , 12h, rtPh B.0 -> Ph90% conversion b-p-dIJ.T,; Sridhar, M. Tetrahedron Lett., 1993, 34,434lI + (x SGTign.;TlOAc , CO, MeCN 80°C, 16h 10% [Pd(OAch/2 PPh3]I L s75% Khalil, H.; Levett, P.; Virica, J.; Sridharan, V. Tetrahedron Lett., 1994, 3.5, 3197Section 179Ketones from Alkenes20310% Pd(OAc), ,20% PPh3 Et4NC1 , CO88% Gring.;Redpath, J.; Sridharan, V.; Wilson, D. Tetrahedron L&t., 1994, 35, 4429 1. Et2BHaSMe2 , ether, 25OC 2. Et$n , neat, O°CPh 3. CuCN.2 LiCl , THF , O°C 4. PhCOCl d Langer, F.; Devasagayaraj, A.; Chavant, P.-Y.; mochel. P, Synlett, 1994, 41084%Me3SiN3, CH2C12,CrQ 59% Reddy, M.V.R.; Kumareswaran, R.; m.Y.D. Tetrahedron L&t., 1995, 36, 67511. [CK12*THF/PhEt2N:BH3, ClOH2w/PhH , CO]: ;5:r36h . 9 4. H202, NaOH , NaOt-BuC~H2JLH. 70%Rao, M.L.N.; Periasamv. M, Tetrahedron Lett., 1995, 36, 90690 A9 w=ma *2 PPh3, DCE d (>20 Lautens. MJ Edwards, L.G.; Tam, W.; Lough, A.J. J. Am. Chem. &..d 1) 99% 1995, 117, 10276204Compendium of Organic Synthetic Methods, Vol. 9Section 1801. Cl$=C=O 2. Bu$nH , AIBN 85% (84:16) Dowd. P,; Zhang, W.; Geib, S.J. Tetrahedron, 1995, 51, 3435 See also:Section 134 (Ethers from Alkenes). Section 174 (Ketones from Ethers).SECTION 180:KETONES FROM MISCELLANEOUS COMPOUNDSConjugate reductions and reductive alkylations of enones are listed in Section 74 (Alkyls from AIkenes). Ph5) 09mPh9 C&Cl20 20°C , 30 min 92%TFP= l,l,l-trifluoropropane Ahamura, A.; Curci, R,; Edwards, J.O. .I. Org. Chem., 1993, 58, 7289#-(-)=NoH ooc,loi?~ * -(-)=o acetone ,80% Olah. G.A,; Liao, Q.; Lee, C.-S.; Prakash, GKSJynlett, PhO3 , CH2C12, -2OC ,2h1993, 427PhN-OH * > Ph Yang. Y.; Li, T.; Li, Y. Synth. Commun., 1993, 23, 1121 N—NHTsPhI(OA&> Ph95%, MeCN , rt , 10 min wPhPh MeMe 87% Zeng, H.; Chen. Z-C, Sytih. Commun., 1993, 23, 2497Section 180Ketonesfrom Misc.205TS-1, H202, MeOH, 4h-NHTS84%TS-1 = titanium silicate molecular sieves Kumar, P.; Hegde, V.R.; Pandey,B.; Ravindranathan. T, J. Chem. Sot. Chem. Commun., 1993, 1553 PhPhKMn04, aq. MeCN , rt , lh N-OH0 *95%k=Wali, A.; Ganeshpure,P.A.; Satish. S&11. Chem. Sot. Jpn., 1993, 66, 1847 NO2NflHdH202K2CO3, MeOH Ballini. R,; Bosica, G. Synthesis, 1994, 723 NNHcoNH2hJ-PhI(OAc);?, aq. MeCN0 w80%P Me Chen, D.W.; Chen, ZC, Synthesis, 1994, [email protected])2Sz& 7DCE reflux , lhChoi, H.C.; m.&Synth.N-OH P +Commun., 1994, 24, 2307Bentoni te/AgzC03 , PhH0 t50%Ph *reflux ,4h Me Me Sanabria, R.; Miranda. R,; Lara, V.; Delgado, F. Synth. Commun., 1994, 24, 2805d=N-NHTs(Bu4N)2S208, DCE , reflux 0lh =c95%Chen F,; Yang, J.; Zhang, H.; Guan, C.; Wan, J. Synth. Commun., 1995, 25, 3163 REVIEW:“Macrocycle Synthesis:Cyclic Ketones,Ketoalkenes,Diketones and Dienes of Ring Size C21 Dang, Y. Org. Prep. Proceed. In?., 1993, 25, 309 to &jr” EQ-;Section 180ACompendium of Organic Synthetic Methods, Vol. 9206SECTION180A: PROTECTIONOF KETONES[Rh(MeCN)3(~phos)l WfhI7acetone, rt ,4hPhJL90%Me / 9 * 00 o= .M, Tetrahedron Lett., 1993, 34, 8071 HSSHn ,-c3m12rt92%Y J Yu, Y.; Lin, R. Org. Prep. Proceed. Int., 1993, 25, 365p-TsOH , PhH , reflux , cat. TMSIDDQ 9H20 C&C12 95% McDon;tld. CL; Nice, L.E.; Kennedy, K.E. Tetrahedron Lett., 1994, 35, 57 MesSid/SiMq OS iMeCF$O$iMe3 , CH2C12 -78OCo=(–bti3LiBF4, MeCN , heat 96% Lillie, B.M.; Avery, M.A. Tetrahedron Lett., 1994, 35, 969 AcCl ,2% SmC13 , rt * 15 min Wu. S.-H.; Ding, Z.B. Synth. Commun., 1994, 24, 2173Section BOAProtection of Ketones207cat. Pd(OAc)z ,2 NaOAc ,02 )OSiMe358%DMSOo= Larock. R.c, Hightower, T.R.; Kraus, GA.; Hahn, I?; Zheng, D Tetrahedron Lett., 1995, 36, 2423Se02 , AcOH , rt ,25 min0 .98%aldehydes can also be used Phx outounian. S.A, Synthesis, 1995, 39CuSO4/SiO2, CHC13 20°C ,2dCaballero, GM.; Gras. E.G,Synth. Commun., 1995, 25, 395Kurihara, M.; Miyata, N. Chem. L&t., 1995, 263See Section 362 (Ester-Alkene) for the formation of enol esters and Section 367 (Ether-Alkenes) for the formation of enol ethers. Many of the methods in Section 6OA (Protection of Aldehydes) are also applicable to ketones.Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)208CompendiumCHAPTER13PREPARATIONSECTIONOF181: NITRILESFROMNITRILESALKYNESNO ADDITIONALSECTION182: NITRILESFROM183: NITRILES HW-hFROMMezC(CN)OHEXAMPLESACID DERIVATIVESNO ADDITIONALSECTIONEXAMPLESALCOHOLSAND THIOLS CN, MeCN , DEAD58%/ C6HlMe. ilk. EL& Synth. Commun.,1993, 23, 2481SECTION184: NITRILESFROMWCHOMeOH, rt* 2. “crude” , MeOH , O°C 2.4 MMPP6 Hz0aCN 88%MMPP = magnesium monoperoxyphthalate R.; Gasch, C.; Lassafwm J-K; Llera, J-M.; Wzquez, TetrahedronLett., 1993,34, 141Ferbdez,185:NITRILES ARYLSMeALDEHYDES1. Me$WI-I2,SECTIONSection 185of Organic Synthetic Methods, Vol. 9FROMNO ADDITIONALALKYLS, EXAMPLESJ.METHYLENESANDSection 190SECTIONNitriles from Halides186: NITRILESFROMAMIDESPh2 PPh3, 2 cc14 Ph20997% CN H other reagents are also given that lead to this conversion Waers. M.A.; Hoem, A.B.; Arcand, H.R.; Hegeman, A.D.; McDonough, C.S. Tetrahedron Lett., 1993,34, 1453 0PhA3 NEt3Ag20, Et1, PhH,25OCSznaidman,M.L.; Crasto,C.; Hecht, SM. Tetrahedron/I(NH2Correia.J, Synthesis,SECTIONPh-CN(dark), MS 4A, 12hNH2Buy-1994,Lett., 1993,34, 1581NaOCl, NaBr, PhWH20 w TBAHS04, [email protected] 1127187: NITRILESFROM82%Bu-C-N55%AMINESNO ADDITIONAL EXAMPLESSECTION188: NITRILESph-OAcFROMESTERSMe$iCN,WPPh& *THF , reflux ,16hPhMCN 98% (E.-Z, >9:1)Tsuji. Y,; Yamada,N.; Tanaka,S. J. Org. Chem., 1993, 58, 16SECTION189:NITRILES FROM THIOETHERSETHERS,EPOXIDESANDNO ADDITIONAL EXAMPLESSECTION190: NITRILESFROMHALIDESAND SULFONATES1. BuLi, THF, -1OOOC 2.ZnI2 , -loo”c + o”c 3. TosCN, -78OC+ rt ,3hCN -Klement,I.; Lennick,K.; Tucker,C.E.; Knochel,P, Tetrahedron84%Lett., 1993, 34,4623210Compendium of Organic Synthetic Methods, Vol. 9MezC(CN)OH , MeCN , TMG *MBrMCNTMG= 1,1,3,3-tetramethylguanidine Dowd. P,; Wilk, B.K.; Wlostowski, M. Synth. Commun., 1993, 23, 2323 TiC4,9-PhgH-CN 93%Ziener. HE,; Wo, S. .I. Org. Chem., 1994, 59, 3838191: NITRILESFROMHYDRIDESNO ADDITIONALSECTION192: NITRILES71%TMSCN , CH2C12 , O°CPhgHClSECTIONSection 194FROMEXAMPLESKETONES1. secBuLi, TMSCl 2. secBuLi1CNck= t-Bu89%3. Me1 4. NaOMealsoworkswith aldehydesubstrates Santiago,B.; u.A.& TetrahedronA 0PhLett., 1993, 34, 58391.Me(Cl)AlNH;! * CF3Kende.AS,; Liu, K. Tetrahedron Lett., 1995, 36, 4035SECTION193: NITRILESFROMNITRILESConjugatereductionsand Michael alkylations of alkene nitriles are foundin Section74D (Alkyls from Alkenes). NO ADDITIONALSECTION194: NITRILESPh—-CN2. t-BuOKFROMEXAMPLESALKENESNO ADDITIONALEXAMPLES85%Section 195SECTIONNitriles from Misc.195:NITRILES FROM COMPOUNDS211MISCELLANEOUS83%Dandgar.B.P%;Jagtap,S.R.; Ghodeshwar, S.B.; Wadgaonkar,P.P.Synth.Common., 1995,25, 2993Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)212Compendium of Organic Synthetic Methods, Vol. 9CHAPTER14PREPARATIONSECTIONSection 196196: ALKENESOFFROMPh-C=r-PhALKENESALKYNES, DMF , 120°C10%Pd(OAc)z,20% PPh3 2 TlOAc ,36h Griw Q, Kennewell,P.; Teasdale,A.; Sridharan,V. Tetrahedron Let?., 1993, 34, 153xz OTsw;(PhMe$i)$uCNLi2 THF , -78OC -3 rtde Marigorta,E.M. Tetrahedron Let?., 1993, 34, 1201 1. *&C3H-W7vrtC3H7$7Cp2Zr(CH2=CH2). Id* -c, 68% 2. H+ . Takahashl,T,; Kondakov,D.Y.; Suzuki,N. Tetrahedron Let?., 1993, 34, 6571(Me$i)$iH , hv (sunlamp) 2h, hexane 70%Pattenden.G,; Schulz,D.J. TetrahedronLet?., 1993, 34, 6787Section 196Alkenes from AlkynesI NO210% Pd(OAc)z 20% PPh3 , DMF TI(OAc) , 130°C 18hI b Et&C‘C02Et Sridharan, V. TetrahedronBrown, S.; Clarkson, S.; Grign.;Le ‘tt., 1993,34,1571.Cp$r(H)Cl , CHg12 20°C ,20 min w 2.5% AgC1410min TBDMSO Wiof. P,; Xu, W. .I. Org. Chem., 1993, Ph/- 0 58,825TBDMSd92%1. t-BuLi , pentane/ether 2. -78OC + rt + -78OC )99% z) Lett., 1994,J.-F, Tetrahedronhv , 1%CpCo(CO)2, PhH, heatStammler,R.; Malacria. SiMe335, 6677-Bu-BuBrasseur,D.; Jestin,J.-L.; NomC02Me1994,23) 69% 54% de1. [email protected] , ether 2.2 eq. BuLi , -4OOC , Me2S 3. NH3/NH&l/ Ph35, 466935,C02Me93%W Synlett, 1994, 921. Cp$rBu2, PMe3 2.35”C , Eto 95c Me$i3OEtEt071%(53:47 cis:trans) 3. H30+ . Takahashl.; Kondakov,D.Y.; Suzuki, N. Chem. Lett., 1994,259 PhNiBr;?-Zn, diphos, H2* phm g2% sakai. &; Takai, Y.; Mochizuki, H.; Sasaki,K.; Sakakibara,Y. Bull. Chem. Sot. Jpn., 1994, 67, 1984Compendium of Organic Synthetic Methods, Vol. 9216Section 197QSiEt3OSiEt3 3% (PCy3)g12Ru=CHCH=CPh2 CHzC12, (0.6 M) ,2X,8hP tie Me Kim, S.-H.; Bowden,N.; mbbs. RcfL J. Am. Chem. Sot., 1994, I16, 10801 Me$iI , Me$n , dioxane SiMe395%61%5% Pd(PPh3)4,25OC,8 h Chatani,N.; Amishiro,N.; Morii, T.; Yamashita,T.; Murd. S,J. Org. Chem., 1995, 60, 1834 OSi(OEt)3 OH-Me20%CpZTi(PMe&, HSi(OEt)3-)&Me 73%Qowe. WL; Rachita,M.J. J. Am. Chem. Sot., 1995, I1 7, 6787 Br SmI2,THF , DMPU P2Phd= 83%Zhou,2.; Larouche,D.; Bennett.SECTION197: ALKENESTetrahedron,FROM1995, 51, 11623ACID DERIVATIVES0.01PdC12(PPh&, PPh3 c6H’-C02HP 250°C, N2c6H1vMiller. J.A,; Nelson,J.A.; Byrne, M.P. J. Org. Chem., 1993, 58, 18 M Cl, Me$i-SiMe3 , toluene5%Pd(dba)z, 80°C,4hObora,Y.; Tsuii. Y,; Kawamura,T. J. Am. Chem. Sot., 1995, 117, 98149840section 199SECTIONAlkenes from Aldehydes198: ALKENES OHFROM217ALCOHOLSAND THIOLSH-montmorillonitedioxane c9H19~ + C9H19d (air free) . reflux ,6h 19) 91% (81 Santhi, P.L.; Siddiqui, M.F. Tetrahedron L&t., 19b3, 34, 1185 -Kantam. OHOH1. SOCl;!, NEt3, 0°C rt NMe(OMe) 2.DBU,0°C + ~PhNMe(OMe)Ph92%T ee) (96.98% Bennani,Y.L.; m.K.B. Tetrahedron Lett., 1993, 34, 2083 Mo(acac)s, dioxane, refluxc lOH23C10H23OH -f* (1+ c1a2Y . 1) 92%Prasad,A.D.; Santhi,P.L. Synth. Commun., 1993, 23, 4;Kantam.;phflp::::::’ wph-/c+ ,,/orrDorta, R.L.; SE.;SECTION73%8%Betancor,C. Tetrahedron Lett., 1994, 35, 5035199: ALKENESFROMALDEHYDESMe 1.2 LDA Et0 2. PhCHO (>98:2 , E:z)Coutrot.Ph,; Grison,C.; Gkardin-Charbonnier, C.; Lecouvery,M. Tetrahedron 2767Lett., 1993, 34,Compendium of Organic Synthetic Methods, Vol. 9Section 199MezCHzPPh3+ BrBuLi , THF , -78OC PhSiMes-Bu [94:6 E.-Z (>98%ee, R)]Bhushan,V.; Lohray, B.B.; En&.D, Tetrahedron Lett., 1993, 34, 50671. H2S, THF , -3OOC 2. NH2NI12 3. -3OOC ,4h C7HlseCHOco1kizo, L .R.; Q&cAC4. MgS04, -3OOC 5. CaCO3, Pb(OAc)d -c7H-IliI 6. THF , reflux 7. PPh3, THF , reflux Jr.. F& J. Org. Chem., 1993, 58, 43 Cfl l~H0,Zr-t , CrCl3, DMFmBr56%(91:9E:Z)Knecht, M.; Boland.W,Synlett,1993, 837CNCH2(CN)2, CdI2,neat PhCHO heaat,5 min95%A PhCN Prajapati,D.; Sandhu.JS, J. Chem. Sot., Perkin Trans. l., 1993, 739 Bu+CH 2Br2 , 25°C Li , CrCl2, DMFII’HFMe020CH0‘,Me02C///n/SnBu3 61%D.M; Boulton,L.T.; Maw, G.N. Tetrahedron Lett., 1994, 35, 2231 wCH0[PPh3=CHMe/I$2NaNTMS23 = *42% (1O:l Z:E)Chen,J.; Wang,T.; aao. K, TetrahedronLett., 1994, 35, 2827SiMe3(Me$i)2CBr2, CrC12 PhCHO &&on.) DMF ,25”CD.M,; Comina,P.J. Tetrahedron84% PhLett., 2994, 35, 9469SiMe3Section 200AIkenes from AlkylsE10*~-Lpp~3+ Cd-J219Br- , dioxaneQH1313CHOPh& , hv , K2CO3, H20, 90°C, 2hYCOEt70% (78:22 E:Z)(withouthv 12:18 E.-Z) Matikainen,J.K.; Kaltia, S.; Hase.T,SynZett,1994, 817 EtOzC/sMe3PhCHO,DMSO tEtO&-WPhcat.CsF, rt + 100°C aed.93%M; Ozanne,N. J. Org. Chem., 1995, 60, 6582SiMe3 PhCHO80%25OC Ph’+ N-4; Staszewski,J.P.; Fuk, D.-K. Tetrahedron Lett., 1995, 36, 3619C02Et 1. KHMDS , THF, lh 5 eq. lg-crown-5,-78OC 0 w / P 2. PhCHO I Ph PhO OPh Ic Tetrahedron+ 4 Ph..(99 A&I.EtOgC02Et1) 98%Lett., 1995, 36,4107C02HMe3SiCH=C=O,BF3GEt2 PJCHO mk.-/P90% (1:l E.-z) T&; Zhang,Y.; Huang,J.; Smith, D.C.; Yates,B.E. Synth. Common., 1995, 25, 15 RelatedMethods:Section207(Alkenesfrom Ketones).SECTIONZOO:ALKENES FROM AND ARYLSALKYLS,METHYLENESThissectioncontainsdehydrogenations to formalkenesandunsaturated ketones,estersand amides.It alsoincludestheconversionof aromaticringsto alkenes.Reductionof arylsto dienesis foundin Section377(AIkene-Alkene).Hydrogenation of arylsto a.Ikanes and dehydrogenations to formarylsareincludedin Section74 (Alkyls from Alkenes).220Compendiumof Organic Synthetic Methods, Vol. 9Section 203CgK , THFWeitz, 1.S.; wov&.M1 J. Chem. Sot., Perkin Trans. I ., 2993, 117 Br Me02FPseudomonas cepacia AC1 100OHCOH* OMe Artaud, I.; Tomasi, I.; Martin, G.; Petre, D.; Mansuy, D. TetrahedronSECTION201: ALKENESRelated Methods:FROMti:H CHO Lett., 1995, 36, 869AMIDESSection 65 (Alkyls from Alkyls). Section 74 (Alkyls from Alkenes). 1. PhLi, THF , 0°C 85%Jurata, H.; Ekinaka, T.; Kawase, T.; gda, M, TetrahedronSECTION202: ALKENESBelier. aFischer,SECTIONH.; Kiihlein,203: ALKENESFROMAMINESK. TetrahedronFROMLett., 1993, 34, 3445Lett., 1994, 35, 8773ESTERS1% Pdz(dba)3-CHC13 ,2.2 HCOOH 2% chiral phosphine , dioxane 1,8-his-(dimethylamino)naphthalene 20°C ,22h :%, ++H MeO,CO Me 96% (85% ee, R) . T,; Iwamura, H.; Naito, M.; Matsumoto, Y .; Uozumi, Y .; Miki, M.; Yanagi. J. w. Am. Chem. Sot.., 1994, 116, 775 02Section 205SECTIONAIkenes from Halides204:ALKENES FROM THIOETHERS221ETHERS,EPOXIDESTe , THFOAcOHLiBHEt3 c Ph Ph DC,; Zhang, Y.; Discord& R.P. J. Org. Chem., 1994, 59, 1004uenishi. J,; Kubo, Y. Tetrahedron65%Lett., 1994, 35, 6697set-BuLi , -78OC+ rt ,90 min 76%BuBuGrDoris, E.; Deschoux, L.; Mioskowski,SECTIONAND205:ALKENESC. TetrahedronFROMBuLett., 1994,HALIDESBu 3.5, 7943AND SULFONATESBu$nH , AIBN , Tol, reflux Ph Destabel,C.; Kilbum, J.D. Knight, J. Tetrahedron Lett., 1993, 34, 3151 9nI ..Li,TI-IF,rt,lh 2. ZnCl;!, THF , O°C-+ rt Brw , THF ,66OCm. 1993,5% “Pd(PPh3)2” , 1Oh T&; Gilbert, A.M.; Huttenloch, M.E.; Min-Min, G.; Brintzinger, 34,3551H.H. Tetrahedron Lett.,Compendium222BrMe$iof Organic Synthetic Methods, Vol. 9MeLi,Section 20620°C 82%-A %k siMe3 Br Bu Bu Baird. M.S; Dale, C.M.; AI Dulayym, J.B. J. Chem. Sot., Perkin Trans. I., 1993, 2c14H16’-eq. MezS=CHz, THFL,1373C14h692% -1OOC + It AIcaraz, L.; Hamett, J.J.; Mioskowski, C.; Martel, J.P.; Le Gall, T.; Shin, D.-S.; Falck, J.R. Tetrahedron Lett., 1994, 35, 5453 Br1. CuCN.2 LiCl , DMPU CSH17ZdC8H1-2. E-hexenyl iodide, 60°C ,12hBu quant.Marquais, S.; Cahiez, G.; Knochel. P,Synlett, 1994, 849 Br Ph L WR.;SmI2,THF,5minPh= i Br Bessho, K.; Yanada, K. Chem. Lett., 1994, 1279I Bu 3SnHPhPhm10% Pd/C , 10% CuI ,20% AsPh3 NMP , 80°C 75 Me0 Me0 Roth, G.P.; Farina, V.; Liebeskind, L.S.; Pena-Cabrera, E. TetrahedronC; Aronica, L.A.; Lardicci, L. TetrahedronSECTION206: ALKENESFROMPh82%Lett., 1995,EtMgBr , THF , O°CMaIan=Ph 95%36,quant. Lett., 1995, 36,9189HYDRIDESFor conversions of methylenes to alkenes (RCH2R’ + 200 (Alkenes from Alkyls). NO ADDITIONALEXAMPLESRR’C=CH2),see Section2191Section 209223Alkenes from AlkenesSECTION207: ALKENESFROMKETONES65%PhMe , 50°CMePetasis. N.A; Bzowej, E.I. TetrahedronLett., 1993,34,943(Me0)2POCHgO2Me 0(-)=yo2t% LiOH , THF , MS , reflux ,4h5c Cardilli, A.; Lattanzi, A.; Orelli, L.R.; Screttri. A, Tetrahedronwsz; 3383t-B+(-)=o -a.$ ~~;;f;;~r2*t-Bu-(-)=newDiels-Aldercatalyst Kobwashi. S,; Hachiya,I.; A&i, M.; Ishitani,H. Tetrahedron Lett., 1993, 34, 3755OTBSArN=Mo(OR)=CHRcatalystOTBSPhH, 20°C,30 min 91% Fu, G.C.; Grubbs. R.H,J. Am. Chem.Sot., 1993, 115, 3800 2Ph-1%Mo[OC(CF&Me]2(NAr)CHCMe2Ph * pl/%/+c6HD89%W-h~Qowe. W.E,; Zhang,Z.J. J. Am. Chem. Sot., 1993, 115, 109981.PhBr , THF , Pd(PPh& NaOH , reflux , 12h 2. NaOH, Hz02P -8,siM!e3L&t., 1994, 35, 27 w17SmI2 PhH/HMPA, rt , 10minPhaI’ O-l/ ()/\ w-h783%siMe3J.&; Colbert,J.C. TetrahedronI I J* dKunishima,M.; Hi&i, K.; Tani, S,; Kato, A. TetrahedronPh76%Lett., 1994, 35, 72538%(PCy3)g1,Ru=CHCH=CPh2 PhH ,55”C, 3hMiller, S.J.; Kim, S.-H.; Chen,Z.-R.; Grubbs.R&J. Am. Chem. Sot., 1995, 117, 2108Section 210Alkenes from Misc.225(96.4)44%W,; Schrisder, F. Tetrahedron Lett., 1994, 35,7935Ni(dppe)Clz,iPrMgBr , THF Me$iCl , rt , (seconds)Ma1 _,; Urso,A.; Lardicci,L. Tetrahedron L&t., 2995, 36, 1133Ar = 2,4-dibromophenyl 68%(97%ee) ; Calabrese, J.C. J. Am. Chem. Sot., 1995, 117, 8992 REVIEW:“Reagent-Controlled AsymmetricDiels-AlderReactions,”Qh.T,; Reilly, M. Org. Prep. Proceed. Int., 1994, 26, 129SECTION210: 0 II 0888q pN t-BuALKENES FROM COMPOUNDSMISCELLANEOUS1. BuLi , THF , -78OC 2. 4.C EtI1lH23C&Me 3. KOt-BuCllH23-Y 5. CeC13,NaBH4 6. THF, 105OC,20h 63x%x93x92% (102:1 E.-Z) Denmark. S.E,; Amburgey,J. J. Am. Chem. Sot., 1993, 115, 10386226Compendium of Organic Synthetic Methods, Vol. 92% Pd(acac)z , BuLi , THF , reflux *Section 210vGoH2170%Gai, Y.; Jin, L.; Jnlia. M.: Verneaux. J.-N, J. Chem. Sot. Chem. Commun., 1993, BuLi9 2%1625Wa~d3O°C +refluxC3H7-C3H7 79% (76:24 E.-Z)Jin, L.; Julia. M.; Verpeaux, J.N. Synlett, 1994, Ph-s-215KOH , Al203 , CBr2F+BuOHPhPhm02Ph96% (Ihan. T.-L,; Fang, SF.; Li, Y.; Man, T.-O.; Poon, C.-D. J. Chem. Sot. Chem. Commun., 1994, 1771Ph02Ph8 eq. SmI2, THF , DMPU 35 minPhwPh95% Ph Keck. Cr.E,; Savin, K.A.; Weglarz, M.A. J. Org. Chem., 1995, 60, 3194OEt s6 IIShimagaki..OEt(E:Z 9:l)Lawesson’s reagent, xylene *reflux ,22hCgH1gwC$117quant. Lett., 1995, 36 7190 M,; Fujieda, Y.; Kimura, T.; Makata, T. Tetrahedron Mg” , cat. HgC12, EtOH SO2Ph5 rt ,2hLee, G.H.; Lee, H.K.; Choi, E.B.; Kim, B.T.; Pak, cI.S, Tetrahedron REVIEW: “Rare Earth Metal Trifluoromethanesulfonates as Water-Tolerated Organic Synthesis,” Kobavashi. S, Synlett, 1994, 679Let?., 1995,98% 36,5607Lewis Acid CatIaysts inCompendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)Oxides from AlcoholsSection 213CHAPTER22715PREPARATIONOF OXIDESThis chapter contains reactions which prepare the oxides of nitrogen, sulfur and selenium. Included are N-oxides, nitroso and nitro compounds, nitrile oxides, sulfoxides, selenoxides and sulfones. Oximes are considered to be amines and appear in those sections. Preparation of sulfonic acid derivatives are found in Chapter Two and the preparation of sulfonates in Chapter Ten.SECTION211: OXIDESFROMALKYNES1. ClPPh2 , NEt3 , THF , -78°C-coMe; Slattery, B.J. Tetrahedror~~k~.,1994, 35, 5137SECTION212: OXIDES 0 IFROMACID DERIVATIVES SnMe3SO2Cl MePhCl, 130°CMe2dNeumann.W.P,; Wicemec,C. Chem. Ber., 1993, 126, 763SECTION213: OXIDESFROMALCOHOLS>(I , -40°c 0 CH2C12 2. airAND THIOLS1. -S-l Gu, D.; mIIN, TetrahedronLett., 1993, 34, 67-so$-I74%228CompendiumSECTION214: OXIDESof Organic Synthetic Methods, Vo19FROMALDEHYDESNO ADDITIONALSECTION215:OXIDES ARYLSFROMEXAMPLESALKYLS,NO ADDITIONALSECTION216: OXIDESFROM217: OXIDESPh-NI OHPhFROMMETHYLENESANDEXAMPLESAMIDESNO ADDITIONALSECTIONSection 219EXAMPLESAMINES0,05 Pr4N Ru04 , 1.5 NM0Ph*?-Ph I %MeCN,rt,2d75% (>50:1 ZE) Goti. A,; De Sarlo, F.; Romani, M. TetrahedronL&t., 1994, 35, 6571H2N-(=)-co2H ,““” * Webb. K&;Seneviratne, V. TetrahedronLett., 1995, 36, 2377SECTION218: OXIDESESTERSFROMNa$02Tol, THF 0.01 Pd(PPh3)4, rt i)Acchiral phosphine ,72hS02Tol..(10 Eichelmann,H.; M.SECTION219:H.-J, TetrahedronOXIDES FROM THIOETHERSGuertin, K.R.; -de.L&OS(=O)Tol 1) 83%Asymmetry, 1995, 6, 643ETHERS,5% TPAP ,3 eq. NM0 MeCN , 30°C, 4A MS ,2h 0+TEPOXIDESTPAP = (n-Pr)fl Ru04 Tetrahedron Lett., 1993, 34, 5369AND92%Section 219Oxides from EthersWW4,229hv (Pyrex)7IPhHsAMe PhHsLCH2QMe92% Ramkumar, D.; $3.nkararaman. S, Synthesis,1057 ?IH202, MeCN , K2C03PhHS-Me Page. PC&,1993,PhHs-Me 82% MeOH, O°C ,2h Graham, A.E.; Bethell, D.; Park, B.K. Synth. Commun., 1993, 23, 1507 Mn02, Me3SiC1, MeOHPh–‘,Me0 II 99% S ’ Me 23, 1759w Ph.Bell&a, F.; Ghelfi. F,; Pagnoni, U.M.; Pinetti, A. Synth. Commun., t-BuOOH, H20, 70°C, 30min BuHS,Bu1993,0 IIB/N Bu J+inmelli. F,; Pellegrino,R.; Pizzo, F. Synth. Commun., 1993, 23, 3157quant.cyclohexanone monooxygenase wPh?*II Ph/‘*73%(99%ee, R) Secundo,F.; Carrea.G,; Dallavalle,S.; Franzosi,G. Tetrahedron Asymmetry, 1993, 4, 1981 1.35eq.oxone * rt, 1.2h with 0.65eq.Oxone- obtain47%sulfoxide We&J&TetrahedronLett., 1994, l‘441.183%35, 3457$3F3.N + FII 95% CHC13, CFC13, -40°C ph/s with 2.7 eq.,obtainthe sulfone(91%) DesMarteau.D.D,; Petrov, V.A.; Montanaari,V.; Pregnolato,M.; Resnati.G, J. Org. Chem., 1994, 59, 2762ph/sC4F9230Compendiumof Organic Synthetic Methods, Vo19NaI04, cat. RuC13eH20 Ph-‘-PhSu. W. TetrahedronSection 219NH Ph-S-Phlh Lett., 1994, 35, 4955quant.NHAc &mcpbaNHAcxfx+x)c(8 Glass. R&; Singh, W.P.; Hay, B.A. Tetrahedron1. Ph/SIMe3)Lett., 1994, 35, kO9H202, ether, DBU , -28OC (-)-camphorsulfonylimine 12. aq. Na sulfite Me. P.CB,; Heer, .J.P.; Bethell, D.; Collington, 1994, 35, 9629quant (35% ee, R) E.W.; Andrews, D.M. Tetrahedron Lett.,NaOCl , TEMPO,Ph”,[email protected] , CH#X2,KBr0 II* PhHs,satd. NaHCO3Me87% Siedlecka, R.; Skarzewski.J, Synthesis, 1994, 401 0 IIPhIO , cat. TsOH , MeCN ,25OC *Ph/‘Me . . avlca82%Ph/‘Me G, Synth. Commun., 1994, 24, 2223 1. Mn02-35% aq. HCl , MeOH 0°C + 10°C, 0.75hPl?0 IIMe99%2. NaOH Ph/‘lMe Fabretti, A.; Ghelfi, F.; Grandi. R,; Pagnoni, U.M. Synth. Commun., 1994, 24, 2393 NaBQ Ph /‘-Me, II, wet zeolite F-90 wIICH2C12, lh PhRSNMe Hirano, M.; Kudo, H.; rvl[orimoto. T, Bull. Chem. Sot. Jpn., 1994, 67, 149282%Section 219Oxides from Ethers231PhIO , MeCN , lh 10% Mn salen catalystPh-‘lMe0 II ‘-MePF57% (62% ee, R) Noda,K.; Hosoya,N.; Irie, R.; Yamashita,Y.; J(atsuki.T, Tetrahedron, 1994, 50, 9609p-Tel/‘+Me0 II HS-Me p-To1chiraloxaziridine, CHg12 t o”c70% ee W .B,; Kochanewyczm,M.J.; Lovely, C.J.; Boyd, D.R. J. Chem. Sot. Chem. Commun., 1994, 25 69PhMezCOOH, Ti(OiPr)d, Hz0 PhjSIMe77% (99% ee,R)II(RR)-DET, CH2C12,-2OOC Ph’ ‘Me Brunel,J.-M.; Diter, P.; Duetsch,M.; Kag;ln. HB, J. Org. Chem., 1995, 60, 8086 1.5M HNO3,1% FeBq ,30 min0 IIB+Bu84%B/Bu Sutiez, A.R.; Rossi,L.I.; Martin, S.E. Tetrahedron Lett., 1995, 36, 1201B4sSiO2, CH2C12,t-B&OH > Bu 30minII S Bu’ ‘Bu86%with 2 eq. t-B&OH, obtain83%of sulfone P.J, Tetrahedron Lett., 1995, 36, 3825 Breton,G.W.; Fields,J.D.; m. cyclohexanone monooxygenase *PhAS’Pasta.P,; Carrea,G.; Holland,H.L.; Dallavalle,S. TetrahedronPhHs,MeNagata,T.; -K.;Ph-S’ II0 97% (54% ee, R) Asymmetry, 1995, 6, 93302 , m-xylene, Mn (III) salencomplex tII66%(51%ee) t-BuCHO, rt Me Yamada,T.; Mukaiyama,T. Butt. Chem. Sot. Jpn., 1995, 68, 3241 Ph”,232Compendium of Organic Synthetic Methods, Vol9SECTION220: OXIDESFROMHALIDESSection 222AND SULFONATESPhi , CuI , DMF , heat PhS02Na Suzuki. H,; Abe, H. Tetrahedron Lett.,SECTION221: OXIDESa 1995,FROM36,PhSO$‘h6239HYDRIDESNO2-03, CH2C12 *Me -1OOC ,3ha; M. From. . .51%(57:2:41o:m:p) Murashima,T.; Kozai, I.; Mori, T. J. Chem. Sot., Perkin Trans. I., 1993, 1591 It; Mori, T. J. Chem. Sot., Perkin Trans. I., 1995, 29 1 arylSuzuki.; FromarylSuzuki.;esters:meta-nitrois themajorproductTomaru,J.-i.; Murashima,T. J. Chem. Sot., Perkin Trans. I., 1994, 2413 acetates:ortho:parapredominates(60:40)Tatsumi,A.; Ishibashi,T.; Mori, T. J. Chem. Sot., Perkin Trans. l., 1995, 339 NO2-03, MeCN, MgO , O°CR = Et R=H95% (14:31:55 0:m:p) 0% . &&,l, H; Yonezawa,S.; Mori, T. Bull. Chem. Sot. Jpn., 1995, 68, 1535 REVIEW:“Ozone-MediatedNitrationof AromaticCompounds with LowerOxidesof Nitrogen,”Mori, T.; &z&i. K Synlett, 1995, 383SECTION222: OXIDESJ5 Olah, GA.;FROMKETONES1. NH20H, PtCl , KOH NO22. CF3C03H(1113exo:endo) Ramaiah,P.; P&ash. CKS, J. Org. Chem., 1993, 58, 76360%Section 225SECTIONOxides from Misc.223: OXIDESFROM233NITRILEShv (254 nm) SO2Ph Li, C.; Fuchs. P.L TetrahedronSECTION224: OXIDES55%MeCN ,25,C, 2h Lett., 1993, 34, 1855FROMALKENESEt* 0-N& EtO’, 09 Bu$nHtoluene, AIBN (syringepump)mBuEtO -Bu EtO-[, 0Balczewski,P.; MikoIajczyk, M. Synthesis, 1995, 392SECTION225:OXIDES FROM COMPOUNDS72%MISCELLANEOUSPhMgBr, THF ,25OC71%i?h Cardellicchio,C.; Fiandanese, V.; Naso.F,; Pietrusiewicz,KM.; WSewski,W. Tetrahedron Lett., 1993, 34, 3135PhCHO t cDc13Oe5MMe2Nt-Bu + Me2NDenmark.SE,; Griedel,B.D.; Coe,D.M. J. Org. Chem., 1993,*58, 988t-Bu234Compendium of Organic Synthetic Methods, Vo19PhO#PhSection 225S02Ph 1. LiNAPH2.Br-. . Yu, J.; Cho, H.-S.; Chandrasekhar, S.; Falck. J.R… Mlmkours)sl. (1, Tetrahedron 35,5437Lett., 1994,0 THF,l-tCardellicchio, C.; Fiandanese, V.; mo. Tetrahedron Lett., 1994, 35, 6343F,; Pacifico, S.; Koprowski,61% (>98% ee, S) M.; &&u.&wicz. K.M.Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)Section 302AIkyne – AlcoholCHAPTER23516PREPARATION COMPOUNDSOF DIFUNCTIONALSECTION 300: ALKYNE – ALKYNE 1. NaNTMS2 ; NBS ~~~‘~~~~-BuMaeriotis. P.pL; Vourloumis, D.; Scott, M.E.; Tarli, A. Tetrahedron L&t., 199;, 34, 2071SECTION 301: ALKYNE – ACID DERIVATIVES NO ADDITIONAL EXAMPLESSECTION 302: ALKYNE – ALCOHOL, THIOLvCHO Brown.;Lo- 1. Bu$nI , -85OC+ 2.3 eq. ZnC12MsO82%ether, 25OC, 15 min 2. H202, NaOH Khire, U.R.; Racherla,U.S. Tetrahedron Lett., 1993,34,15 % +9 %O°C3.iPqCHO -*OHBu 89% (98:2 antisyn)Katsuhira, T.; Barada. T,; Maejima, K.; Osada,A.; Qku. A, J. Org. Chem., 1993, S&6166Compendium of Organic Synthetic Methods, Vo19236Section 302(946) 80% Zhang, L-T.; MO, X-S.; Huang, J-L.; Huang. Y.-Z< Tetrahedro;r Lat., 1993, 34, 1621 000, 01.2 eq. LDA, THF, -1OOOC 2.2 eq. PhCHO , THJ?p-To Y3. NaH ,THF , O°CI zsiAk3Kusuda, S.; Kawamura, K.; Ueno, Y.; Toru.Ph 83% (>99%ee, S) Tetrahedron Let?., 1993, 34, 65871.3 eq. t-BuLi 2. EtCHO , -78OC +II Ph.-3OOC *k Ph Cl Satoh, T.; Hayashi, Y.; Yamakawa.;>ePh 67%Bull. Chem. Sot. Jpn., 1993, 66, 18661. o-DCB , reflux2. TBAFJin, J.; Smith, D.T.; weimb.SKJ. Org. Chem., 1995, 60, 5366(PhCd&AlEt2’Na+PhCHO To1 , O°C , lhPh>ePhOH Ahn, J.H.; Joung, M.J.; Yoon. N.M, J. Org. Chem., 1995, 60, 617395%Bu-Bu C8HlYSmI2, HMPA/PhHBu 78% Kunishima, M.; Tanaka, S.; Kono, K.; Hioki, K.; Tani, S, Tetrahedron Let?., 1995, 36, 3707Alkyne – AmineSection 305237t-BuCHO , Ga13, NEt3 PhPl?TfWfi 80% Han, Y.; Huanae. Y.-7, Tetrahedron L&t., 1995, 36, 7277 PhSnBu3PhCHO;>el’hInC13 , MeCN ,25OC ,30 min 92% Yasu&, M.; Miyai, T.; Shibata, I.; Baba, A,; Nomura, R.; Mats&a, H. Tetrahedron Let?., 1995, 36,9497 PhCHO , Zn , THF+ satd. NH&l,Ph>Phxrt(89 -I.;Riazi-Kermani,F. Synth. Commun., 1995, 2.5,SECTION 303: ALKYNE SPh292311) 68%- ALDEHYDE 1. s02C12,cc4, o”cFortes. CC;+ PWCHO 2. CuC12, [email protected] Garrote, C.F.D. Synth. Commun., 1993, 23, 2869SECTION304: ALKYNE47%Ph—==—-/- AMIDE NO ADDITIONALEXAMPLESSECTION 305: ALKYNE – AMINE 2 Et2NH2, 1% CuCl(““”THF , 50°C, 2h Imada, Y.; Yuasa, M.; Nakamura, I.; &&K&K&. F2BWuJJ.-L;NEt2S.-L J. Org. Chem., 1994, 59, 2282SiMe3OHYan, D.-S.; Tsai, H.-W.; Chen, S.-H. Tetrahedron Let?., 1994, 35, 500391%238Compendium of Organic Synthetic Methods, Vol9BuNH2,3%gBrSection 307CuBr , MeCN b90%Geri, R.; Polizzi, C.; Lardicci, L.; Qporusso. A.m Gazz. Chim. Ital., 1994, 124, 241Okita, T.; hobe. M, Tetrahedron, 1995, 51, 3737SECTION306: ALKYNE- ESTER NO ADDITIONALSECTIONPhu307: ALKYNE- ETHER,EXAMPLESEPOXIDE,THIOETHER!-c) PhSeSePh L* Ph- CZC-SePh 75% CuI , HMPA Reckziegel, A.; Menezes, P.H.; Stefani, H.A. Tetrahedron Let?., 1993, 34, 393=C-Br &;PhSeBr , CuI , DMF W-4-HC5H,lpSPh82% Silveira, C.C.; Reckziegel, A.; Menezes, P.H. Tetrahedron Let?., 1993, 34, 8041Braga. a;PhI(OAc)2, PhSeSePh , CH2C12 PhPhSePh4o”c 81%Tingoli, M,; Tiecco, M.; Testaferri, L.; Balducci, R. Synlett, 1993, 211 0I / HOOCOCF3, MeCNDBU , CuC12e2H20 , O°C// 483% Godfrev U-D,; Mueller, R.H.; Sedergran, T.C.; Soundararajan, N.; Colandrea, V.J. Tetrahedron Let?., 1994, 35, 6405Section 311SECTIONAlkyne – Alkene308: ALKYNE239- HALIDEk:1;;&&velmV,; Rollin, Y.; G&&henne, C.; Gosmini, C.; P&ichon, J. Tetrahedron L&t.,1994, 35, 4777(collidine)$P-H Brunel, Y.; JXouw. SECTIONPF6Ph75%G, Tetrahedron Lett., 1995, 36, 2619309: ALKYNE- KETONEJ-c Cl‘*Ph7NW *2. FVP (5OO*C) ~R.A.;PlPh72% x 82%H&ion, H.; Janosi, A.; Raut, S.V.; Seth, S.; Shannon, I.J.; Smith, F.C.Tetrahedron Lett., 1993, 34, 5621SECTION310: ALKYNE- NITRILE1. CuCN , TMSCl , H20 DMSO , MeCN ,72h P-H2. cat. NaI , 50°C uo. F.-T%;Wang, R.-T. Tetrahedron Lett., 1993, 34, 5911SECTION311: ALKYNE 2P-CN72%- ALKENE 10% Pd(OAc)2, 30% PPh3 THF , reflux , lh% &Iandai. T,; Tsujiguchi, Y.; Matsuoka, S. Tetrahedron Lett., 1993, 34, 761596%Compendiumof Organic Synthetic Methods, Vol9240Section 311co EtSiMe3Pd(dba)z, Ph3As NMepyrrolidone , 40°COTf90%2, aq. HCl B.H,; Alami, M. Tetrahedron Lett., 1993, 34, 1433mhutz.0.05 Pd(PPh)4, 0.1 CuI 2eq.N&,PhH,lh Gueugnot, S.; Linstrumelle, G. Tetrahedron Lett., 1993, 34, 3853w-h1 5Alaml.;/–OHc511, Pd(PPh3)4,15minM Ferri, F.; m. 93%G, Tetrahedron Lett., 1993, 34, 64031. norbomadiene, Bu3Sn = Ph 1% PdC12(PPh3)2,80-100°C, 20h Phi 2. heatPhKosuni. M,; Kimura, T.; Oda, H.; Migita, T. Bull. Chem. Sot. Jpn., 1993, 66, 3522 1. Cfl 11, Pd(PPh3)4, CuICl a;Cl2. PdC12(PhCN)z,piperidine rtCrousse,B.; Linstrumelle, G. Tetrahedron Lett., 1994, 35, 3543phtph n. It&;FVP (500°C)Boeters, C.; Morrison, J.J. J. Chem. Sot., Perkin Trans. l., 1994, 247359%Section 314Acid – AldehydeSiMe3241Me3Si 1. set-BuLi , THF , -45OC 2.ZnBr2 -45OC + 20°CSW33. H30+ SiMe3-8-85%I… Nonnant. J.-F,; Platzer, N. Tetrahedron Lett., 1994, 35, 5645Meyer, C.; uPh Ph 5% HRh(CO)(PPh3)3 35% PEt3 BuH+ THF , reflux ,9h 68% (>20: 1 endo:exo)Yamzguchi. M,; Omata, K.; Hirama, M. Tetrahedron Lett., 1994, 35, 5689PhSnBu3, Dibal , THFYClNi(acac)z , P(OEt)3 yrefiux 77% Cui, D.-M.; Hashimoto, N.; Ikeda. S,; Sato, Y. J. Org. Chem., 1995, 60, 5752SECTION 312: CARBOXYLICACID – CARBOXYLICNO ADDITIONALSECTION 313: CARBOXYLICACIDEXAMPLESACID – ALCOHOL,THIOL1.1:3 TiCldLiAlH4, lh CFC13 , THF , -5°C 2. aq. HCl 62% Garcia, M.; de1 Campo, C.; Sinisterra, J.V.; Llama, E.F, Tetrahedron Lett., 1993, 34, 7973SECTION 314: CARBOXYLICACID – ALDEHYDENO ADDITIONALEXAMPLES242Compendium of Organic Synthetic Methods, Vol9SECTION 315: CARBOXYLICSection 316ACID – AMIDEMe M&J444,1.2.2 LDA , ZnC12 2. HJO+0/ A 0 Ta.FYN w-rcog-I 86% (88% de)U+; Maier, S. J. Chem. Sot. Chem. Commun., 1995, 199 15 eq. LDA ,2.5 eq. Al(OiPr)370% (98% ds/86% ee) J(azmaier. ‘IJ,; Krebs, A. Angew. Chem. Int. Ed. Engl., 1995, 34, 2012SECTION 316: CARBOXYLICA?–ACID – AMINE1. PhMgBr , THF , -40°C 2. TFA , CH2C12C02EtI BoC3. DDQ , CH2C12 4.10% NaOH , refluxC02H-l+’ H83~72~93% UJ.; Pedregal, C.; Rubio, A.; Valenciano, J.; Navio, J.L.G.; Alvarez-Builla, J.; Vaauero. u Tetrahedron Lett., 1993, 34, 63171. Ph//““”OSiMe3NHPh OSiMq, ZnBr2, CH2C12 C02H2. H30+ 84% (35:65 syn:anti)]Mladenova. M,; Bellassoued, M. Synth. Commun., 1993, 23, 725Section 318Acid – Ether243Nc /“@Me~~~~h~~~~ep) (02H+ ‘“) (02H derivative, 25OC,40h 2.6N HCl(94 T, Tetrahedron Lett., 1994, 35, 2713Soloshonok, V.A.; m.HONH2HoNH26)CO2H 1, oxaIy1chloride , ether 2. satd.NaHC03, refIux 3. TsNHNH2 , reflux 4. NaE3H4,THF98x39% HGuan, X.; Borcb=irdt,Tetrahedron Lett., 1994, 35,3013REVIEWS:“RecentDevelopmentsin the StereoselectiveSynthesisof a-Amino Acids,” b&&r.R-Q,Tetrahedron, 1994,50, 1539“RecentStereoselectiveSynthetic Approachesto P-Amino Acids,” Cole. IX,Tetrahedron,1994,50,9517Section315 (Carboxylic Acid – Amide). Section344 (Amide – Ester). Section 351 (Amine – Ester).RelatedMethods:SECTION 317: CARBOXYLICACID – ESTERNO ADDITIONAL EXAMPLESSECTION 318:CARBOXYLIC THIOETHERACID – ETHER, EPOXIDE,C02H ..(85 1 0 Mead. K.T; Pi&& SK. Tetrahedron Let?., 1993, 34, 6997C02H 15)82%244Section 322Compendiumof Organic Synthetic Methods, Vo19SECTION 319: CARBOXYLIC OzHb ACID – HALIDE, SULFONATE1.2.2 eq. see-BuLiKMEDA THF , -9OOC 2.4 eq. c13cc13 , THF , -78OC3.4N HCl / F Moyroud, J.; Guesnet,J.-L.; Bennetau,B.; Mortier. J ISECTION 320: CARBOXYLICACID – KETONE 98% (>98% ee)Na , n-C3H70H, refluxMoody, H.M.; Kantein. B,; Broxterman,Q.B.; Boesten,W.H.J.; Kamphuis, J. Tetrahedron Lett., 1994, 35, 1777 0.5 C~(ClO4)24 Hz0 02, MeCN ,rt ,lO-15h **OH 0 &sy.96%J,; Belotti, D.; Bellosta, V.; Brocca, D. Tetrahedron Lett., 1994, 35, 6089 Also via: Section 360 (Ketone – Ester).SECTION 321: CARBOXYLICACID – NITRILENO ADDITIONAL EXAMPLES Also via:Section 361 (Nitrile – Ester).SECTION 322: CARBOXYLICACID – ALKENE1. CFz=CHLi 2. H30+NC”3 H O+ l* *c02HTellier. F,; Sauvetre,R. Tetrahedron Lett., 1993, 34, 543360% (E)245Alcohol – AlcoholSection 3230.1 pcy3,3 TESCIzs g;*lbkC~A/ c3*&,’c3H–[email protected], T.; Baba, Y .; Inanaga. J, J. Org. Chem., 1993, 58, 299=o=’MnZnBr’ether;FDuchsne. A; Abarbi, M.; Pamin, J.-L.; Kitamura, M.;,!402H Noy~ri,R. Synlett, 1994, 524Section 313 (Alcohol – Carboxylic Acids). Section349 (Amide – Alkene). Section 362 (Ester- Alkene). Section 376 (Nitrile – Alkene).Also via:SECTION 323: ALCOHOL, THIOL – ALCOHOL,PhCHO ,SmI2,*ph%phTHIOLphhcHo OH 1%97% in THF + 2.8 eq. HMPA 10% Shiue, J-S.; Lin, C-C.; J%ng. J-M, Tetrahedron Lett., 1993, 34, 335 ~3W~N)6Bu9 K2C03But-BuOH , H20,12hN 6~J.A,;60%OH 89%ODHQSiMe380%) 9 OS04HOKSiMe3 (89% ee)DHQ = dihydroquinidine ODHQRane, A.M.; L6pez, C.J. Tetrahedron Lett., 1993, 34, 1893 AD-mix-PphoN-t-BuOH , H20, 0°C PhO&OH 95% Tetrahedron Lett., 1993, 34, 2267 Wang, Z-M.; Zhang, X-L.; SharPless.246Section 323Compendium of Organic Synthetic Methods, Vol9MeMe Rh+2 cat. , Cs2CO3 , PhBrOH Barrett. A.G.w; Itoh, T.; Wallace, E.M. Tetrahedron Mt., 1993, 34, 22332 Lebrun, A.; &my.1.2 eq. SmBr2 2. Hz0J-I,; Kagan.90% Tetrahedron Lett., 1993, 34, 2311DHQ-CLB Me3SmC$-i11Me& 93%(71%ee,R) 6H Zargarian, D. Tetrahedron ktt., 1993, 34,Okatnoto, S.; Tani, K.; &Q. F.: ~K.B.; 2509 1. Ph$iSH , NEt3, MeOH P2. TBAF, AcOH-,,i-lt/OH..(7 Brittain, J.; m.pASH1)Y, Tetrahedron Lett., I993, 34, 3363 H20, 10 KBar , 60°C, Id *QH E93% (49% ee) Kotsuki. H,; Kataoka, M.; Nishizawa, H. Tetrahedron Lett., 1993, 34,4037 7l%Os04,1%catalystcatalyst = bis-dihydrquinolylCrispino, GA.; Jeong, K.-S.-; Kolb, H.C,; Wang, Z-M.; Chem., 1993, 58, 3785derivative87%247Alcohol – AlcoholSection 323OHH 1.10% Cp$QCl;! , ether / 2.5 eq. EtMgCl ,25OC, 12h 3. 02,OKEt-cc-r70% (98:2 syn:anti)Hovevda. A.J&; Morken, J.P. J. Org. Chem., 1993, 58, 42371%OS04,l-t,3K2c&OHOallyl3 K3Fe(CN)6,3 MeSO$H2,t-BuOH-Hz0 82% (39% ee, R) Am. Chem. Sot.,Morikawa, K.; Park, J.; Andersson, P.G.; Hashiyama, T.; VJ. 1993, 115, 8463 1. Li powder, CH& 5% 4,4’-di-t-Bubiphenyl THF , -4OOCCHO2. H20 +Y52%Guijarro, A.; Yus. M, Tetrahedron Lett., 1994, 35, 253(955)93%Adam. WJ Gevert, 0.; Klug, P. Tetrahedron L&t., 1994, 35, 1681 ’ OH AD-mix f3 , aq. t-BuOH , O°C phw5r PhSPhWalsh, P.J.; Ho, P.T.; King, S.B.; wss.+ OH (98% ee, 2S,3R) K.B. Tetrahedron Lett., 1994, 35, 5129Ph 75%Section 323Compendium of Organic Synthetic Methods, Vo19248+wph*o/Jph955 synmi O (94% ee, syn)21%50% ee, SH Kaneko, Y.; Matsuo, T.; I(,ivooka. S, Tetrahedron Lett., 1994, 35, 4107Yb-TMS-BrOTMSfl!p62%THF-HMPA TMSO ; Nakahashi, M.; Kuno, T.; Tsuno, M.; Makioka, Y.; I&&i. Tetrahedron Lett., 1994, 35,411l .K.: Fujiwam Y,0 t-BUSH, hvC6H13UMe57% (4:l syn:anti) Newcomb. M,; Dhanabalasingam, B. Tetrahedron Lett., 1994, 35, 5193 Ph0.1 Kz0~04 ,3 MeSOflH2K3k(cN)6,3 K2C03OHO°C , 12hR = cinchonidine Corey. EJ.; Noe, M.C.; Grogan, M.J. Tetrahedron Lett., 1994, 35, 6405 NbC13, THF , rt 2 t-BuCHO71% (>95:5 d,l:meso) zvmoniak. J,; Besangon, J.; MoIse, C. Tetrahedron, 1994, 50, 2841Alcohol – AlcoholSection 323Al,KOH,MeOH,rt,5minPhCHO24987% (1:l d,l:meso)Ph PhOH Khurana. J.M,; SehgaI, A. J. Chem. Sot. Chem. Commun., 1994, 571 1. dIpczBH , ether , -78OC 2. PhCHO , -78OC *3. NaOH , Hz02PhL= = AH76% (>95% ee)Brown. H.C,; Narla, G. .J. Org. Chem., 1995, 60, 4686 P$*n l&N,PhPh/Ph e/OPh* BH3, THFPh 3 OH (16% meso:RR+SS (99% ee SS)Quallich. G.J,; Keavey, K.N.; WoodaIl, T.M. Tetrahedron Lett., 1995, 36, 4729 CHOCHOBu$nH , PhH ,2O”C hvtaOH OH46% (98: 1 cixtrans)Hays, D.S.; Fu. G.C, J. Am. Chem. Sot., 1995, 117, 7283 Phes 9 t-BuOH , H20, &Fe(CN)e* Ph K2CO3, (DHQDhPHAL , K~OSO~)OH)~OH 95% (97% ee , R)Torii, S.; Liu, P.; Tanaka, H. Chem. Lett., 1995, 319 REVIEWS:“Synthesis of cr.,@-Alkenediols.A Review,” Patwardhan.S.A, Org. Prep. Proceed. Ink, 1994, 26, 645Section 325Compendiumof Organic Synthetic Methods, Vol9250“The Oxygenation of Vinyl Cyclopropanesas an Entry Into Stereoselective1,3-Diol Synthesis,” Feldman. Synlett, 1995, 2 17 “Catalytic Asymmetric Dihydroxylation,” Kolb, H.C.; Van Nieuwenhze, M.S.; SharPless. K.B. Chem. Rev., 1994, 94,, 2483Also via:Section 327 (Alcohol – Ester).SECTION 324: ALCOHOL,Section 357 (Ester – Ester).THIOL – ALDEHYDE1. PhCHO , NEt3 *II-CHO+)-cO2H2. H30+ I51% Barco, A.; Benetti, S.; De Risi, C.; Pollini, G.P.; Spalluto, G.; Zanirato, V. Tetrahedron Lett., zp34, 39071993,[RhCI(CO)& , 1-methylpyrazoIe HSiMe2Ph , CO (50 atm) Fukumoto, Y.; Chatani, N.; Murai. S, J. Org. Chem., 1993, 58, 4187 09vp)c cs /“7Ph$=CHOMe , CHCl3,2XCHOC6H13Yu, L.; uC6H13QH s = = -CHO77%ZAJ. Chem. Sot. Chem. Commun., 1993, 232Section 330 (Alcohol – Ketone).RelatedMethods:SECTION 325: ALCOHOL,mo2NA ClTHIOL – AMIDE1. EtCHO , Li(powder) 3% C1()Hg,THF 2. H20 *m-92N71% OHRam6n, D.J.; Yus. M, Tetrahedron Lett., 1993, 34, 7115 NHTs 3m.aq.NaOH, 100°E (-hJ,; Bats, J-P.; Hautefaye,P.; Nuhrich, A.; Lamidey, A-M.Tetrahedron Lett., 1993, 34, 2315,o~5%Section 325Alcohol – Amide251MeS02NH2, t-BuOH , Hz0 rt , AD-mix-pTM *mtPh96% (96% ee)mt2OH AD-mix-pm= 5% DHQDz-PHAL (chichona alkaloid-phthalzine reagent),2% K~OSO~(OH)~ Bennani, Y.L.; -less. KB, Tetrahedron Lett., 1993, 34, 2079 COzMe1. Dibal , -78OC 2.NHCbzOTMSH OMe 3. TiCl2(OiPr)z*ACO&k= = = INHCbzCO2Me2s66%10%K yooka. S.; Suzuki, K.; Shirouchi, M.; Kaneko, Y.; Tanimori, S. Tetrahedron Lett., 1993, 34, 5;29HO Me2CuLi , Me (96 Reetz. M.T,; Riilfing, K.; Griebenow, N. Tetrahedron Lett., 1994, j5, 19691. BuLi , -78°C 2. LiNaphth , -78°CpBz3. PhCHOme2FHBzp +(1 Foubelo, F.; Yus.4)84%OH!Ph..1) 72%Tetrahedron Lett., 1994, 35, 48311. LDA , THF , -78°C 2. CeC13,THF , rt* PhnfMe2 3. PhCHO , THF , -78OC 0 OH Shang, X.; Liu. H.-J,Synth. Commun., 1994, 24, 248568%. H 3) 66% (97 Taniguchi, M.; Fujii, H.; Oshima. K.: Utimoto, K, Bull. Chem. SO;. Jpn., 1994, 67, 2514252Compendiumof Organic Synthetic Methods, Vol9Section 326hvNfw-b3-G0 HOjJ86%0 w-h3 Dlttarm., Xu, F.; Qi, H.; Martin, M.W.; Bordner, J.; Decosta,D.L.; Kiplinger, J.; Reiche, P.; Ware, R. Tetrahedron Lett., 1995, 36, 4197 .CL(CHzO), , acetone, K2CO3 ) ON 0 N 0 N H20, ultrasound I H d OH Jouglet, B.; Oumoch, S.; Rosseau.G, Synth. Commun., 1995, 25, 3869SECTION 326: ALCOHOL,[email protected]%THIOL – AMINE1. LDA , TiC12(OiPr)2 THF * 2. t-BuCHO , THF 3. H30+Et02C&phEt02Aph6HPh(>99OH :1)78%jfKanemasaI S,; Mori, T.; Wada, E.; Tatsukawa,A. Tetrahedron Lett., 1993, 34,677 OH Ph Ph2 TsNCO , THF , Id 2% Pd[P(OiPr)&reflux OHXu, D.; -less.K.B Tetrahedron Lett., 1993, 34, 951l- WSiMq, SnC14CH2C12,O°C,30 min 2.TBAF,m(1.Hioki. H,; Okauda,M.; Miyagi, W.; It& S. Tetrahedron Lett., 1993, 34, 61311.1) 74%253Alcohol – AmineSection 326Keck. G&, PaIani, A. Tetrahedrdn Lett., 1993, 34, 3223 H4r H5 eq. TABH , AcOH/MeCN MeMe-35OC +P &+22”C* NHOBn TABH = Me+JH BH(OAc)3 Osterhout, M.H.; Reddy, J.P. Tetrahedron Lett., 1993, 34, 3271 N-OBnDA;Ph-Br2 eq. SmI2, THF-HMPA CHO t N=C , -15OC, 3h91%Murakami, M.; Kawano, T.; Ito, H.; Ito. Y, J. Org. Chem., 1993, 58, 1458H 1. LDA 2. PhCHOPhmn2Lagu, B.R.; Crane, H.M.; m.NBn2(80:20, R)D.C, J. Org. Chem., 1993, 58, 4191 EtzNzCu(CN)Liz , THF0 -78OC + rtN. Y,; Asao, N.; Meguro, M.; Tsukuda, N.; Nemoto, H.; Sadayori, N.; Wilson, J.G.; Nakamura, H. .I. Chem. Sot. Chem. Commun., 1993, 1201254Compendium of Organic Synthetic Methods, Vo19Section 326Yb(OTf)3, NHEt2 CH&C6H1397%,20 min mt2w-h3> 99% a-attack Chini, M.; Crotti, P.; Favero, L.; Macchia, F.; Pineschi, M. Tetruhedrun Lett., 1994, 35,433 C8HEt2NH , LiBF4, MeCN 80°C , 18h* c8H1ym.YOH Chini, M.; Crotti. P,; Favero, L.; Macchia, F. Tetrahedron Lett., 1994, 35, 761 bCbZCbZ79) 52%(21&&,Q. T,; Tajiri, IS.; Harimoto, T.; Ninomiya, I.; Kiguchi, T. Tetrahedron Lett., 1994, X5,2205 HH CH3N02 ,2 eq. AlC13 w 8O”C, 5h/““” 70%Sarton,;Bigi, F.; Maggi, R.; Tomasini, F. Tetrahedron Lett., 1994, 35, 2393 Ph I N /1. Li, cat. cl(jf&j 2. PhCHO *3. H20Almena, J.; Foubelo, F.; Yus. MJ.0 o=68%PhHN-Phvarious electrophiles were used Org. Chem., 1994, 59, 3210 93% (1:l)MeCH=N-OMe , iPrOHsono.& /* e’NHOMeT,; Kise, N.; Fujimoto, T.; Yamanami, A.; Nomura, R. J. Org. Chem., 1994, 59, 1730Section 326Alcohol – Aminec”, f”’1. BH#Me2,255c’)THF2. MeOH45%3. H202, NaOH w-h1C&9Goralski. CT%;Hasha,D.L.; Nicholson, L.W.; Zakett, D.; Fisher, G.B.; Singaram. B, Tetrahedron L&t., 1994, 35, 3251 0Sm , Me$iCl/NaI , MeCN rt, 15minOHPhq-p 72%Akane, N.; Hatano, T.; Kusui, H.; Nishiyama, Y .; Ishii. Y cJ. Org. Chem., 1994, 59, 7902NBn2mn2(92:8 RS)90%with LDA(63:7 R:S) 90% Lagu, B.R.; Liotta. DC, Tetrahedron Lett., 1994, 35,4485l.BMS,THFJ5 ~c.T.;3. H202, NaOHHasha,D.L.; Nicholson, L.W.; Sine.R, Tetrahedron Lett., 1994, 35, 5165OH ultrasound,Al(Hg) , aq. THF 2h iJo Fitch, R.W.; Luzzio. F.A, Tetrahedron Lett., 1994, 35, 601392% NH2Section 326Compendiumof Organic Synthetic Methods, Vol9256t-BuNH2 , CH2C12 5% Yb(OTf)3, rt ,16h c8H~~mt-Bi8H~~;Bu m99 P,; Favero, L.; Macchia, F.; Pineschi, M. Tetrahedron Lejt., 1994, 35, 7089 Bn IBn I1. Cp$Zr(Bu);!, THF -78OC+ rt ,4h OMe2. BF3aEt2, THF , O°C 3. aq. NaOH82% (>98:2 syn:anti)Ito, H.; Ikeuchi, Y.; Taeuchi. T,; Hanzawa, Y.; Shiro, M. J. Am. Chem. Sot., 1994, 116, 5469 Na,iPrOH,THF76% (erythro/threo = 0.8)Bartoli, G.; Cimarelli, C.; Palmieri. G, J. Chem. Sot., Perkin Trans. I., 1994, 537, SmI2Q+ ‘0I /THP , HMPA85%Booth, SE.; Benneche,T.; Undheim. K, Tetrahedron, 1995, 51, 3665 Ph 0NHPhPhNH2 , TiC13, PhCHO THF/CH$12, Py , rt *M-+Clerici, A.; Clerici, L.; porta 0, Tetrahedron L&t., 1995, 36, 59559 % HO PhPh 76%Section 327Alcohol – Ester257OHBnNH2,lOkbar ,CH2C1290% cat. Yb(OTf), , rt ,6d Meguro, M.; Asao, N.; mote.030s=Nt-Bu , DME ,25OC PhwPhNHBnY, J. Chem. Sot., Perkin Trans. I., 1994, 2597quinuclidine , 36hNH?-Bu- Ph+ph+ Phqph OHOH..(973)Rubinstein, H.; Svendsen,J.S. Acta Chem. Stand. B., 1994, 48, 439 1. TFAA, CHg12 rt ,4h OH2. K2CO395%Fontenas,C.; Bejan, E.; Haddon, H.A.; Belavoine, G.G.A,Synth. Commun., 1995,25, 629SECTION 327: ALCOHOL, OBn = =THIOL – ESTERCHOCO2Me3% LiC104, -30°C CHg12, 4hOSiMe2cBu..(92 Reetz. M.T,; Fox, D.N.A. Tetrahedron Lett., 1993, 34, 11198)>84%EtOH , CO, NaBr , iPr2NEt-I.;Pd2(C4H7)& , maleic anhydride ‘) H*co2Et Maruyama, T.; Makuta, T.; Yamamoto. A. Tetrahedron Lett., 1993, 34, iI35MePhCHO ,5% SmI2,5 minPhCH2C12, -78OC -$< OTMS Van de Weghe, P.; Collin, J, Tetrahedron Lett., 1993, 34, 3881C02Me OTMS95%258Compendiumof Organic Synthetic Methods, Vol9/LOHYeast, pet. ether, H20 C02EtSection 327rt, IdAC02Et58% (94%ee) Yeast = Saccharomyces cerevisiae Jayasinghe,L.Y.; Smallridge. A.J,; Trewhella, M.A. Tetrahedron L&t., 1993, 34, 3949 0C02Me Mn(OAc)[email protected](OAc)pHzO9%78%25OCix-OHOMeOshima, T.; Sodeoka,M.; Shibasaki,M. Tetrahedron L&t., 1993, 34, 8509 . ;co2MeNHC02t-But-Buo2cJ-t &Me$‘h w.‘.~~ao~~;a~ 2.5% aq. HCl0 i bHJ&; Zhang, J. J. Org. Chem., 1993, 58, 294 OSiMe3 I PhCHOPhm12C02Meer. LB, .I. Org. Chem., 1993, 58, 2324 TMsOMe92%p-MS10% [Cp2Zr(Ot-Bu)THF][BPh4]:=C02MePTMS +&CO$Ie I= Z s=CH2C12, PhCHO , rt , lh -^(..(1.11)95%Hong, Y .; Norris, D.J.; Collins, S, J. Org. Chem., 1993, 58, 3591 1. LDA 2. Et2AlC1OH/COzt-Bu *56%xx 2’ (84:16 syn:anti) m. S&; Fried, J.A.; Grassl, Y.N.; Marolewski, A.E.; Pelton, E.A.; Poel, T.-J.; Rezanka, D.S.; Whittaker, M.R. J. Org. Chem., 1993, 58, 7304 3* ‘sSection 327Alcohol – Ester259BrCH2C02Et, PhTeLiKeC13 C02Et ether, OOC +rt 95%Fukuzawa. S.-i; Hirai, K. J. Chem. Sot., Perkin Trans. I., 1993, 1963 oxido reductase from Geotrichum candidumC02EtQH 0 = EC02Et500 mM bis-TRIS-HCl 24h , NaDPH , ADH , glucose93%(>99% de; 92% ee) Kawai. Y,; Takanobe, K.; Tsujimoto, M.; Ohno, A. Tetrahedron Lett., 1994, 35, 147 PhCHOI-(,, TBSO~e/wI-MP ()pMpCH2C12, -78’C+ OTBS (6PMP = p-methoxyphenylUOPMP &TBS 94) 95% 92%ee..Kobayashi. S,; Kawasuji, T. Tetrahedron Lett., 1994, 35, 3329 OH 3 eq. CH2=CHC02MeCOzMe1.2 MgBr2 , CH2C12 O°C , lh 58% (> 20~1 endo:exo) Woo. SH, Tetrahedron Lett., 1994, 35, 3975 TMSooka. S,; Kido, Y.; Kaneko, Y. Tetrahedron Lett., 1994, 35, 5243260Compendium of Organic Synthetic Methods, Vo19BnOCH$HOSection 327,5% binolTiC12toluene , O°C ,2h . -K.;81% (94% ee, R)Matsukawa, S. J. Am. Chem. Sot., 1994, 116, 4077 0CaMeMeOH , Amberlyst-15 ,2Oh96% 0 bd.OH* c c R.c; Selvapalam, N. Synth. Commun., 1994, 24, 2743 OHC II–CO2iRL = chiral imine ligand Hayashi, M.; Inoue, T.; C)euni. N, .I. Chem. Sot. Chem. Commun., 1994, 341o=Br/co2Et, THF ,2hLVT, rt(-pco2EtLVT = low valent titanium 67% Aoyagi, Y.; Tanaka, W.; Ohta. A, J. Chem. Sot. Chem. Commun., 1994, 1225 1. BuLi , ether, -4OOC 2. PhCHO2”H w3.03 , CH2C12, -78°C 4. Me$Ph*CO2 Me51% Hormuth, S.; &i&&H.-U.; Dorsch, D. Liebigs Ann. Chem., 1994, 121 RuBr&hiralC02MemM.J.;bis-phosphine)60 psi H2 , aq. MeOHOH = = z &COzMequant. (99% ee, S) Harper, T.G.P.; Kalberg, C.S. J. Am. Chem. Sot., 1995, 117, 4423Section 328Alcohol – Ether261VO(OAC)~ , PhH , TBHP -A Pho//O” 98%Choudary, B.M.; Reddy, P.N. Synlett, 1995,959 Also via:Section 313 (Alcohol – Carboxylic Acid).SECTION 328:ALCOHOL, THIOL – ETHER, EPOXIDE, THIOETHERE+Z. 1) (18 Mandai. T,; Ueda, M.; Kashiwagi, K.; Kawada, M. Tetrahedron Lett.: 1993, 34, 1110 0Uozumi, Y.; w.1. 0.1% [PdC1(rtC3H5)]2 0.2% R-MOP, HSiCl3H RMOP b 65 x 83%(g5% ee) T, Tetrahedron Lett., 1993, 34, 23351. BH#Me2, Me2S , O°C 2. aq. NaOH , Hz02 3. NaOHmder.=3 .OMe40°C, 24h 2. KF , KHC03, Hz0278%G,&; Bobbitt, K.L.t .I. Am. Chem. Sot., 1993, 11.5, 7517pm2Section 328Compendium of Organic Synthetic Methods, Vol92621. BuCHO , Li(powder) 5% DTBB , THF, O°C 2 H oEtQc1H EtgK87%BuGuijarro, A.; yuS. n& Tetrahedron Lett., 1993, 34, 3487‘-“’cat BF3 OEt2 .42%Mark& I.E.; Bayston, D.J. Tetrahedron Lett., 1993, 34, 6595phxph2 eq. BHpSMe2 2 eq. TMSOTfBartels, B.; Hunter. R, J. Org. Chem., 1993, 58, 67567 PhSH , SiO2;;;p+ z&SPh20°C, 20hMe3SiCdJ1389% Raubo, P.; wC&1314%a-h3J, Synlett, 1993, 25 ClCH2SPh , SmI2 t(-KS,,o=73% Yamashita, M.; Kitagawa, K.; Ohhara, T.; Iida, Y.; Masumi, A.; Kawasaki, I.; Ohta. S, Chem. Lett., 1993, 6531. PhONa , DMFA0PhOTOBn2. HCl-H20 k/OBnCwlsen. P.H.J*; Aase, K. Acta Chem. Stand. B., 1993, 47, 617OH 81%Section 328Alcohol – Ether263cat. FeC13, MeOH ,25OCPhOH0.75h90%N,; Salehi, P. Synthesis, 1994, 1152OH eq. eq. CH2C12, 12h , rt -2. HOONa 1.3Re207 ,92,6-lutidineOF78%OHBoyce, R.S.; Kennedy, R.M. Tetrahedron Left., 1994, 35, 51331. SO(Im)2 OH 2. PhO- Li+OH34% OH D, Tetrahedron Lett., 1994, 35, 6279El Arabi Aouad, M.; El Meslouti, A.; Uzan, R.; mere. OHOH PhthNSCl , CHC13 , 60°C, 4dSNPhth64%Me0precursor to o-thioquinones Capozzi, G.; Menichetti. S,: Nativi. C,; Simonti, M.C. Tetrahedron Lett., 1994, 35, 9451v HMarson.;HgO , dil. H2SO4 , 20°C WllWll-*OH 73% Harper, S.; Wrigglesworth, R. J. Chem. Sot. Chem. Commun., 1994, 18791. t-BuLi , THF , -78OC 2. cyclohexanone ~T,.A,;HO Dullweber, U.; Branan, B.M. Heterocycles, 1994, 37, 18775%264Compendiumof Organic Synthetic Methods, Vo191. Bu$nCH(OEt)z, BuLi THF , -78OCPhCHOSection 328PhCH(OEt)z2. aq. NH4ClOH 65% Parrain, J.-L.; Beaudet,I.; Cintrat, J.-C.; Duch$ne, A.; Quintard. J.-P,Bull. Sot. Chim. FL, 1994, 131, 304(CFcO2)Re03 , O°C 2,6-lutidine , CH2C12McDonald. FL; Towne, T.B. J. Org. Chem., 1995, 60, 5750-OHPhSeCl , CHCl3 -LO,= = XePhW Cooper, M.A.; Ward. A.D, Tetrahedron Let?., 1995, 36, 2327L,, ..= = bH 36) quant.OH OH88%2.H20Corey. EL; Palani, A. Tetrahedron Let?., 1995, 36, 3485J&l.S,; Cho, C.M. Tetrahedron Let?., 1995, 36, 4845HOSection 329(3-I265Alcohol – Halide1.2% Cp2Ti(O4ClC&& , toluene 1% TBAF , Al2O3,5 PMHS , rtw-hOH2.1M NaOH , TI-IF* u PMHS = polymethylhydrosiloxane 94% (70:1) SLJ. Am. Chem. Sot., 1995, 117, 12641 Verdagauer,X.; Berk, S.C.; md. 0BF3GEt2, NaBH3CN 6h .0IOH 87%Stlkrrshna. &, Viswajanani, R. Tetrahedron, 1995, SI, 3339 OMee’ , MeOH, aq. MeCN , Bu&IClO4 lhOH 96%Safavi. A.: Iranpoor. NJ Fotuhi, L. Bull. Chem. Sot. Jpn., 1995, 68, 259 1 REVIEW:“Metal-Catalyzed Direct Hydroxy-Epoxidation of Olefins,” Adam. W,; Richter, M.J. Accts. Chem. Res., 1994, 27, 57SECTION 329: ALCOHOL,THIOL – HALIDE, SULFONATE1. LDA. ZnCl2 , THF . -78OC mcl2. PhCHO80%Cl Mallaiah, IS.; Satyanarayana,J.; Ila H,; Junjappa,H. Tetrahedron L&t., 1993, 34, 3145a; 58,486. 77) 74% (23 Furutani, H.; Ansari, M.H.; Sakai, T.; Utaka, M.; Takeda, A. J. Org. Chem., 1993,266Compendiumof Organic Synthetic Methods, Vo19Section 3291. DibaI , CHg12, -78OC [email protected]%2.ZnBr2, BussF CHzCl2, 40°C T,; Hayashi, H.; Yamanaka, H. Tetrahedron Lett., 1993, 34, 5777. ma.MgBr2, Bu$IBH4 -ether/CHglz:72%‘-Ph +.Ph 22% “Ph Bailey, P.L.; Briggs, A.D.; Jackson,R.F.W.; Pietruszka,J. Tetrahedron Mt., 1993, 34, 6611 Mg(NO& , Bu4NBr ,5h CHC13OHY.-Q, Koo, B.-A.; Ko, J.-A.; Cho, Y.-S. Chem. Lett., 1993, 190793%NaI04, NaHS03Masuda, H.; Takase,K.; Nishio, M.; Hasegawa,A.; Nishiyama, Y.; Ishii. Y, J. Org. Chem., 1994, 59, 5550 Lick , DMF , 70°C , IdPh-,jPhJ/H (35+Lc1 ..65)Nymann, K.; Svendsen,J.S. Acta Chem. Stand. B., 1994, 48, I83 BrPhCHOOH CN9 InCN84% (56:44 erythro:threo)Araki, S.; Yamada, M.; Butsugan. Y, BUZZ.Chem. Sot. Jpn., 1994, 67, 112690%Section 330Alcohol – Ketone267REVIEW:“Regioselectiveanbd ChemoselectiveSynthesisof Halohydrins by Cleavageof Oxiranes with Metal Halides,” m. C,; Righi, G. Synthesis, 1994, 225 SECTION330: ALCOHOL,THIOL- KETONERawal. VH,; Krishnamurthy, V.; Fabre,A. Tetrahedron Lett., 1993, 34, 2899 M F3P 0,,15 min 96% Curci, R.; D’Accolti, L.; Detomaso,A.; Fusco, C.; Takeuchi. K.; Ohga, Y.; Eaton.& Tetrahedron Lett., 1993, 34,4559 TIPSPhCHO , Me& rpsp”88%WPh Shoda,H.; Nakamura,T.; Tanino, K.; Kuwajima, I Tetrahedron Lett., 1993, 34, 62811. Me$i(OTf)Z , NEt3 m &2. PhCHO ; Nishio, K. .I. Org. Chem., 1993, 58, 2647HO*78%(919syn:anti)Ph OAcOAc RuC13,MeCO# MeCN – Hz0 – CH2C1278%Murahashl. S.-I,; Saito, T.; Hanaoka,H.; Murakami, Y.; Naota, T.; Kumobayashi, H.; Akutagawa, S. J. Org. Chem., 1993, 58, 2929Compendium of Organic Synthetic Methods, Vol9xcSection 3300 0’ acetone >96%o”cOHOH (>98% ee , R)D’Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci. R, J. Org. C&m., 1993, 58, 36000 II1. BuLi , CO, -1lOOC THF/pentane/ether 2. rt , H30+ Hui, R.C.; Wang, W.-L. J. Org. Chem., 1993, 58, 5843Sevferth.;H PhCHO ,5% Sc(OTf)3, aq. THF *Ph Y 83%,; Hachiya, I.; Ishitani, H.; Araki, M. Synlett, 1993,472PhPhCHO 2%9 CH2C12W&)3PhUPh 84%Ishihara, K.; Hananki, N.; Yamamoto. HJynlett,1993, 5770 PhwcHoHMPA,rt,THF, SmI2 *Ph*0 83% (83:17 antixyn)Miyoshi, N.; Takeuchi, S.; Ohgo, Y. Chem. Lett., 1993, 959 -MeC03H , cat. OsC13Phv0I-IPhvMeCN-H20-CH2Q . Murahashl. S.-L; Naota, T.; Hanaoka, H. Chem. Lett., 1993, 176762%269Alcohol – KetoneSection 330PhCHO , A1203 ultrasound, 22h..(77 Ranu, Ike,23) 75%Chakraborty, R. Tetrahedron, 1993,49, 5333PhCH2CH0 CHOPhkPh;H20, SmI2 OH?)H(3961) 64%Miyoshi, N.; Takeuchi, S.; Ohgo, Y. Chem. Lett., 1993, 21291.==cPhCHOBu, EtCN , -78OC20% chid acyloxyborane 2. aq. HCl= =BuPha81% (85% ee, R) Ishihara, K.; Maruyama, T.; Mouri, M.; Gao, Q.; Furuta, K.; Yamamoto. H, Bull. Chem. SOC. Jpn., 1993, 66, 34831. 2.2 eq. SmI3 , tetrahydropyran 2. propanal 3. H30+95%955(trans:cis)J.-L; Colomb, M.; Kagan, H.& Tetrahedron L&t., 1994, 35, 1723OHTFA , CDC13 ) 2dph 0Dmhoux.;Doris.Tetrahedron Lett., 1994, 35, 2017270Compendium of Organic Synthetic Methods, Vol9a PhSection 330Cl86%3 eq. pyridineC02MeAraneo, S.; Clerici, A.; Porta. 0, Tetrahedron Lett., 1994, 35, 2213P hlOHp)-(=)-oHClcat. HZSM-5 DCE , reflux67%HZSM-5 = acidic zeolite [SiO$A1203 = 401 Paul, V.; Sudalai, A.; Daniel, T.; Srinivasan.V, Tetrahedron Lett., 1994, 35, 2601 01. LDA , THF , -78OC 2. (iPrO)$Cl 3. acetone ,II Ph 7, -78OCOH 5 1% conversion (88% yield)4. aq. NH8a.W,; Mtiller, M.; Prechtl, F. J. Org. Chem., 1994, 59, 2358 OHPhCHO , 10% Sm(hmds)J -30°C) 18hSasai, H.; Arai, S.; Shibasaki. M, J. Org. Chem., 1994,UI -“iMeVS.;PhCHO , Yb(OTf)3OHaq. THF, rt , 19hHachiya, I. J. Org. Chem., 1994, 59, 3590Ph 9 1% (73:27 syn:anti)271Alcohol – KetoneSection 3301. Me3A1, PhSeH 2. Me$=CHCH2CHO92%x62%3. BusnH, hvI.-Y.C,; Lee, J.H.; Lee, H.W. Tetrahedron Lett., 1994, 35, 4173 OHl.NaHMDS,THF * 2. PhCHOPhPh(946)69%Goh, J.B.; Lagu, B.R.; Wurster, J.; J,iom. DC, Tetrahedron Lett:, 1994, 35, 6029 H 01, LHMDS , toluene-hexane t-Bu2. Y(OTfl3,HIIIIII -OOC, 18ht-Bux,99% 0 crou. P,; Di Bussolo, V.; Favero, L.; Macchia, F.; Pineschi, M. Tetrahedron Lett., 1994, 35, 6537 i FfKfR-BINAPIPh-, PhC12SiSiMe3,PhH Ph* w3+4. HBF4 5. H202 Matsumoto, Y.; Hayashi. T,: Ito, Y. Tetrahedron, 1994, SO, 335OH73~78%, Yb(OTf-)3, 0°C 0PhCHOPhiPrmt , ether, 3h92% (34:66 threo:erythro)Fukuzawa. S.-i,; Tsuchimoto, T.; Kanai, T.. Bull. Chem. Sot. Jpn., 1994, 67, 2227Compendiumof Organic Synthetic Methods, Vol9272JrPhSection 330OTMS OzMe -=c MeBuflClOd , e’SnBu3Ph=Yoshida. L; Morita, Y.; Ishichi, Y.; Ime. S, Tetrahedron Lett., 1994, 35, 5247dPhEnbolm.;Sm1z2Br94%f”fPhSchreier, J.A. J. Org. Chem., 1995, 60, 1110 PhCHO , MS 4A, 13h 5% PdClz[R-DINAPI-AgOTf *23°CPhu;Phufi87%9%Sodeoka,M.; Ohrai, IS.; Shibasaki. m J. Org. Chem.,1995, 60, 2648‘: 0, acetone, IX, ld 92%OH 0 Bovicelli. Pa;Lupattelli, P.; Sanetti, A.; Mincione, E. Tetrahedron Lett., 1995, 36, 3031OHC Zn(NO3)2, acetoneHo Me2NCH2CH20H 30°C ,6hpH 10.1 pH 11.098% 0%Buonom. ET,; Rosauer,KG.; Dai, L. Tetrahedron Lett., 1995, 36,4o$I0% 100%Section 330Alcohol – Ketone2731. Bu$nH , AIBN, PhH relux0 -Ph2. PhCHO, 10°C, 12hti73% (61 erytrho:threo) Enholm. EJ,; WhitIey, P.E. Tetrahedron Lett., 1995, 36, 91571. SmI2 BrM%5 42. Hz0OHPh Y77% O Arime, T.; Takahashi, H.; Kobayashi, S.; Yamaguchi, S.; Mot-i. N, Synth. Commun., 1995, 25, 389 DMSO , KSF , microwave, 3 min Ph / . . lllemrnOH 055%DJ Hammadi, M. Synth. Commun., 1995, 25, 3141 0Sm.Ph *1. LDA 2. Ti(OiPr)$l53%3. TBHP, BaO 4. NH8 , Hfl m; Kluge, R.; SchiiBer, M.; Hoffmann, G. Tetrahedron, 1995, 51, 3175 OH$ A (CH2)7Cl3CCO2H , 11°C , Cl2 , MeOH wh9EtOH, NaHC030 w98%k (CH2)7CgHWTassirznon. P.S.&; De Wit, D.; De Rijk, T.C.; De Buyck, L.F. Tetrahedron, 1995, 51, 11863Br-COzEt1.2 q. SmI2, -6OOC –+ -5O.C * 2. cyclohexanone , -50°C -+ 0°CcC02Et OHUtimoto. &; Matsui, T.; Takai, T.; Matsubara, S. Chem. Lett., 1995, 19798%274Section 33 1Compendium of Organic Synthetic Methods, Vo191. AlMe I Ph Aoki, Y.; ‘crPh 79% (13:87 erythro:threo)2. PhCHO iI(.: Uti moto. K, Chem. L&t., 1995,463PhPhCHO-78OC ,6.5h Ishihara, K.; Hanaki, N.; Funawashi, M.; Miyata,M.; Yamamoto. 1995, 68, 1721SECTION 331: ALCOHOL,THIOLPh Bull. Chem. Sot. Jpn.,- NITRILE3: 1 EtCN-CH2C12, 1Oh 20% Mg-dihydrooxazolidinec&3-cHo Corev.EJ.; ww,OMS catalyst E * ca13>cN 12% bis-dihydro oxazolidine derivative z. Tetrahedron Lett., 1993, 34, 4001 HCN92h9* 100 units enzyme O.lM citrate bufferNCHOacN93%Jz;Fonenzyme = hydroxynitrile lyase from Hevea brasiliensis Klempier, N.; Ga; Hayn, M. Tetrahedron Lett., 1993, 34, 476980% Ohno, H.; Mori, A.; m. 0288% (95%=, 9S, Chem. Lett., 1993, 975 1. LiCH2CN 2. H30+ *[email protected]%;fIaye. TJL; Crawford, K.B. J. Org. Chem., 1994, 59, 520Section 33 1Alcohol – Nitrile2751. TMSCN , CH2C12 , rt KCN/18-crown-62. MeOH/THF , SmI2H”-(=)-cN 80%Olson, S.H.; Danishefskv. SL Tetrahedron Lett., 1994, 35, 7901 OH 51. LDA , THF , -78OCOH CNph-CN 2. PhCHOPh TCN +Ph hcPh Ph . 1) 70% (5 5 Carlier. P.R; Lo, KM.; Lo, M.M.-C.; Williams, I.D: J. Org. C’hem.,‘1995, 60, 7511 OH [ LDA , PhCH2CN ] , TMSClCNPhCHO97%Zhou, J.J.P.; Zhong, B.; mennan.Ph Rh J. Org. Chem., 1995, 60, 2261 HOPhCHO Me$iCN, Ti(OiPr)d 72% (91% ee, S)Balm. C,; Miiller, P. Tetrahedron Lett., 1995, 36, 1625GoI~~~-~H~ tm;Cl Cl Zhmg, X.-L.; Han, Y .; Tao, W.-T.; Huann. Y .-2, J. Chem. Sot., Perkin Trans. l., 199% 189 Review:“Catalytic Asymmetric Cyanohydrin Synthesis,” North. M, Synlett, 1993, 807276Section 332Compendium of Organic Synthetic Methods, Vo19SECTION 332: ALCOHOL,THIOL – ALKENEAllylic and benzylic hydroxylation (C=C-C-H -+ C=C-C-OH, etc.) is listed in Section 41 (Alcohols from Hydrides).2 MeMgBr , CuCN BF3QEt2, THFBnBn -78OCOH E z=Me88%S-L; Lee, D-H.; Sim, H-S.; Lim, J-S. Tetrahedron Lett., 1993, 34,91 1. TIPSCl 2. MeLi -L PhCHOJNEt2 yJ+L–ywyj&L 81%Tsukazaki, M.; Snieckus. V, Tetrahedron Lett., 1993, 34,411 Lee, J.; Tsukazaki, M.; Snieckus, V, Tetrahedron Left., 1993, 34, 415 2SmI2,r-t 2 t-BuOH , THFMe0Me0Me05 +CHO 7r(2 OH..OH1) 66%Glllmann. T, Tetrahedron Lett., 1993, 34, 607SPhBuLi , THF , -78OC tC5HllOH Takano. S,; Sugihara, Y.; Ogasawara, K. Tetrahedron Lett., 1993, 34 8455% DTBB , THF, O°Conly product (90%)OHD.&; Kim, K.; Martinez, J.P. Tetrahedron Lett., 1993, 34, 3071 1. PhCHO , DMF , 0°C wSC13., OH = = Q = = = t.97)Kobavashi. S,; Nishio, K. Tetrahedron L&t., 1993, 34, 345310 eq. BuLi , 10 min )89%71%OHBuLautens. M,; Gajda, C. Tetrahedron Lett., 1993, 34, 4591 BI-j/-BrrJC&CHO, EG-Zn eDMF , O°C ,2hC3H372% EG-Zn = electrogenerated reactive zinc Tokuda. M,; Mimura, N.; Karasawa, T.; Fujita, H.; winome. 7607H, Tetrahedron L&t., 1993, 34,PhCHO , hv (>320 nm) EtCN , -78°C ,5h E-snBu3A+&+ EthPh (30muwa…k; Shiigi, J.; Nishigaichi, Y. Tetrahedron Mt., 1993, 34, 345770) (86: 14 E.z)278Compendium of Organic Synthetic Methods, Vo19Section 332Et2Zn , Ti(OiPr)d , 12h -6OOC + -55OCd 8%,Ti(OiPrb(93% ee)Rozema, M.J.; Eisenberg, C.; Liitjens, H.; Ostwald, R.; Belyk, K.; wel. LAt., 1993, 34, 3115P, Tetrahedron1,2dichlorobenzene , 12h reflux , CO.5torrllllI~lll90%bHOH Janardhanam, S.; Devan, B.; RaiogoDalan. K, Tetrahedron L&t., 1993, 34,676l 1. Sharpless epoxidation 2. TsClPh OH78% (>90% ee)3. Te , LiBHEt3 , THF TBAF,lt* – D-c; Discordia, R.P.; Zhang, Y.; Murphy, C.K.; Kumar, A.; Pepito, A.S.; Wang, Y. J. Org. Chem., 1993, 58, 718 BuiPrMgBr , THF BuwJP)2Ni2c12Ducoux, J.-P.; LeMenez, P.; tine&Bu *(CH2)2CH20Hu-mCH20H (>25 1) 60 N… Wenkert. E, J. Org: Chem., 1993, 58, 1290MeJSiSnBu3 , DMF 86%CsF, rt, lh *b mu;OH Isono, N.; Kaneta, N.; Shibasaki, M. J. Org. Chem., 1993, 58, 2972Section 332Alcohol – Alkene279OH whv,CO,THF,8hc. CA;75Xu, D.; Gladstone, B.G. J. Org. Chem., 1993, 58, 538EtMgBr , 10% Zr complex THF ,25*CMorken, J.P.; Didiuk, M.T.; Hove-OTMS65% (>97% ee) A.H, J. Am. Chem. Sot., 1993, 115, 69975% (binol)TiClz , BnOg-CHO C02Bn Me63% (99:l syn:anti; 99:l ZE; 99% ee, R) Mikami. K.; Matsukawa, S. J. Am. Chem. Sot., 1993, 115, 7039‘* –cbvSiMe3 ’ “:‘igchiral ligmdphuPhCHOZ = = 63% (92% ee)(96:4 erythro:threo) bH Ishihara, K.; Mouri, M.; Gao, Q.; Maruyama, T.; Furuta, K.; Yamamoto, H,J. Am. Chem. sot., 1993, 115, 11490 2. TBAFOH –i=h’, 10% Pd(OAc)z2 Na02CH ,2 BuflCl ,2 iPr2NEt MezNCOMe ,8O*C, Id ~R.c.;Ding, S.; Tu, C. Synlett, 1993, 14570% (5644 E.-z)280Compendium of Organic Synthetic Methods, Vo19Section 332x= Sin&ton.D.A,; Redman, A.M. Tetrahedron Lett., 1994, 35, 509&,gmak. J.D,; Geng, B.; Uang, S.; Strickland, J.B. Tetrahedron Lett., 1994, 35, 985 1. Cp$Zr(H)Cl , CH$12 2. Me2ZnBum3. PhCHO , O°CBu 94%WiDf. P,; Xu, W. Tetrahedron Lett., 1994, 35, 5197 //oO2eq. Me#=CH2,THF-1OOC + rt 80% OH Alcaraz, L.; Hamett, J.J.; Mioskowski, C.; Martel, J.P.; Le Gall, T.; Shin, D.-S.; Falck, J.R. Tetrahedron Lett., 1994, 35, 54490 /1. ($-C$-I,hTiCl iPrMgC.1, THF , -50°C 2. PhCHO , -50°C += -20°[email protected][email protected] (1.441) 42%Szymoniak, J.; Felix, D.; Moi’se. C, Tetrahedron Lett., 1994, 35, 86131. HSiC13 , cat. Pd(PPh& 2* PhwCHo , DMFKobavashl, . S .; Nishio, K. Synthesis, 1994, 457Ph 87% (>99: 1 syn:anti)Section 332Alcohol – AIkenephCN,Nyluene9281refhx, 3hwfiMe 73% Ph(3:2 synxnti)Kim. S,; Cho, C.M. Tetrahedron Lett., 1994, 35, 8405Pd(OAc)z ,3 PPh3 , PhH 7O*C, 16hCHO-5OH 47% Watanabe, T.; Sakai, M.; Miyaura, N.; Suzuki, A,.!. Chem. Sot. Chem. Commun., 1994,467 OHBuMgBr N-NHTs* .,,t5L Takhi, M.; Yadav, J.S. Tetrahedron Lett., 1995, 36, 307Chandrasekhar.,1. Li , NH3 , THF-EtOH 2. TBAF , THFBu, -78OC* ,, ,*’ *3.30% aq. H202, KHCO3 , MeOH OH Taber. D.F*; Yet, L.; Bhamidipati, R.S. Tetrahedron Lett., 1995, 36, 3515% Pdz(dba)3*CHC13 , THF 20% PPh3 , heat MpM(,oOH93% KanG S-K,; Park, D.-C.; Park, C.-H.; Hong, R.-K. Tetrahedron Lett., 1995, 36, 405 Phs1. Cp2TiClz/2 BuLi , 0°C 2-ma.PWCHOT,; Miura, I.; Horikawa, Y.; Fujiwara, T. Tetrahedron Lett., 1995, 36, 1495282Compendiumof Organic Synthetic Methods, Vol9Section 332Co(tdcpp) = [5,10,15,20-tetrakis(2,6-dichlorophenyl) porphinato] Cobalt (II) -Y.; Sugamoto, K.; Nakama, T.; Sakamoto, T.; Matsui, T.; Nakayama, M. Tetrahedron Lett., 1995, 36, 18’79 PhPh 3 t-BuOK, BuLi THF , -78OCOH *R=TBS (79 R=H (20 Tomooka, K.; Keong, P.-H.; Nakai. T, Tetrahedron L&t., 1995, 36,.. .21) 48% 80) 90%&891. BuLi, THF , -78°C 2. PhCHO, -78OC -+ rtPhxH/= 85%MO, X.-S.; uuang. Y.-Z, Tetrahedron Lett., 1995, 36, 3589OMe Dibal , 14% Ni(cod)z 20% R-BINAP , lh i-lOMehtens.78% (97% ee) M; Chiu, P.; Ma, S.; Rovis, T. J. Am. Chem. SOC.,1995, 117, 532‘OMeAldehyde – AmideSection 335283Ph SnCb-NBu3 , MeCN reflux Yamaguchr. b&; Hayashi, A.; Hirama, M. J. Am. Chem. Sot., 1995, 117, 1151S.-K,; Park, D.-C.;Rho,H.-S.; Yu, C.-M.; HowJ.-H,Synth. Commun., 1995, 25,203 OMe =cPhCHO .9 10%Ti(OiPr)d20% chiral binaphthylamineBemsford.C, Angew. Chem. Znt. Ed. Engl., 1995, 34, 1717Also via:Section 302 (Alkyne – Alcohol).SECTION 333: ALDEHYDE- ALDEHYDENO ADDITIONAL EXAMPLESSECTION 334: ALDEHYDE- AMIDES02PhSO2Ph Brown, S.; Clarkson, S.; Grigg. RJ Sridharan, V. J. Chem. Sot. Chem. Commun., 1995, 1135SECTION 335: ALDEHYDE- AMINE Cl DMF , POC13 8%Balasundaram, B.; Venugopal, M.; Permumal.P.T, Tetrahedron Lett., 1993, 34,4249284Compendium of Organic Synthetic Methods, Vo19SECTION 336: ALDEHYDE- ESTERNO ADDITIONALSECTION 337: ALDEHYDEEXAMPLES- ETHER, EPOXIDE, THIOETHERctWp-OMe)2KOD)210 eq. PPh3 , CO, H2+ HC(OEt)3 ,2d (96 + HC(OEt)3 + PPTS ,12h (0 Femandez, E.; B. S, Tetrahedron Lett., 1994, 35, 2361 2% Pd(PPh3)4,5 atm CO, THF C5Hll4) loo)PhSH , 70°C , 16hEt0 quant. quant.CHCHO PhSOgawa. &; Takeba, M.; Kawakami, J.; Ryu, I.; Kambe, N.; &poa 1995,82% (13:87 E.-Z) N, J. Am. Chem. Sot.,117, 7564SECTION 338: ALDEHYDE- HALIDE, SULFONATENO ADDITIONALSECTION 339: ALDEHYDESECTION 340: ALDEHYDEEXAMPLES- NITRILENO ADDITIONALSECTION 341: ALDEHYDEEXAMPLES- KETONENO ADDITIONALEXAMPLES- ALKENEFor the oxidation of allylic alcohols to alkene aldehydes, also see Section 48 (Aldehydes from Alcohols).CHO1. Cp$r(Cl)CH=CHOEt cat. AgClO42.H3O+ oMaeta, H.; Suzuki. K, Tetrahedron Lett., 1993, 34, 341OEtC5h *Section 341285Aldehyde- AlkeneSection 341Li 1.OMe-78OC+ 0°CPhCHO 2.1NCHO PHCl , OmC75%Duhamel, I,,; Duha.mel,P.; Le Gallic, Y. Tetrahedron Lett., 1993, 34, 319OTMS 0 IOTMSCAN, MeCN , O°CPaolobelli, AX; Latini, D.; Ruzziconi.25%CHOTetrahedron Lett., 1993, 34, 721polymeric Fe catalystSaha,AK.; Hossain. M.M, Tetrahedron Lett., 1993, 34, 3833 BrCHO 69 (3-W& 79%cyclic B catalyst, -78°C ,8h(99:l exxendo) ,92% ee Corev. E.J,; Loh, T.-P. Tetrahedron Lett., 1993, 34, 3979PhCHOCsF-DMSO , rt + loO°CPWCHOZnClz, rt ,2h &; Salemkour, M. Tetrahedron Lett., 1993, 34, 528170%2.md.7=-iPhCHO ,5% TfSiMe3 CH2C12, rt ,15hv MqSi CHO OSiMe3 Duhamel. L; Gralek, J.; Bouyanzer, A. Tetrahedron Lett., 1993, 3% 774580%Com~n~um of Organic Synthetic Means, Vol9286N-t-Bu md.WI,: 1187PhCHO , 10% ZnBrz , THF(Me3Si)zHC J a; Majidi, A. J, Org. Chem., 1993, 58, 2517 m/CHOSection 341SnBq, CgHlyBr, AIBN20 atm. CO, PhH , 80°C, 8hYamazaki, H.; Ogawa, A.; Kambe, N.; ma.1.9 074% N, J, Am. Chem. Sot., 1993, 115,, acetonea2. PH3P=CHCH0, CH2C12‘“~0, 84%Adger, B.J.; Barrett, C.; Brennan, J.; McGuigan, P.; Wervey. Commun., 1993, 1220M.A, J. Chem. Sot. Chem.HO , SmI2,25OCCHO (955 Van de Weghe, P.; collin,[1,4:1,3])72%Tetrahedron Lett., 1994, 35, 2345Bu 1. Bu$H , TiCI , CH2Cl2 2. F’OC13 , DMF , O-5OC67%CHOAsokan. CV,; Mathews, A. Tetrahedron Lett., 1994, 35, 258575 Derien, S.; Dixneuf. P.I-I, J. Chem. Sot. Chem. Coals.,25) 85%: 1994, 2551Ph-OH287Amide – AmideSection 342Pd(PPh3)4 , NH4PF6 , toluene – phmcHo 02 , heat90% Gomez-Bengoa, E.; Noheda, P.; Echavarren, A.M. Tetrahedron Lett., 1994, 35,7097 Et0SnBu,1,PhCHOph/n/CHOBF3mOEt2, CH2C12, -78OC, lh 86% Cabezas, J.A.; Oehlschlaner. AC, Tetrahedron Lett., 1995, 36, 5127Mn02, hexane, 15 mmph-N,OHphmCHo 87%Shinada, T.; Yowa.L Tetrahedron Lett., 1995, 36, 6701 CHO Ru (indene)Cl(PPhg)z88%-i_iPhPhTrost, B.M.; Livingston, R.C. J. Am. Chem. Sot., 1995, 117, 9586 CHO2% [ Rh(CO)z(acac) ] +C3H-W72.2% biaryloxyl phophiteJohnson, J.R.; Cuny, G.D.; mwald.SLAngew.A C3H7w785% Chem. Int. Ed. Engl., 1995, 34, 1760Also via P-Hydroxy aldehydes: Section 324 (Alcohols – Aldehyde).SECTION 342: AMIDE – AMIDE NO ADDITIONALAlso via Dicarboxylic Acids: DiaminesEXAMPLESSection 312 (Carboxylic Acid – Carboxylic Acid) Section 350 (Amines – Amines)288Compendium of Organic Synthetic Methods, Vol9Section 343SECTION 343: AMIDE – AMINE Me C=NAcCl , Ac20 , HCl 63%100-130°C) 4hNHAc Me Vijn. R.J,; Arts, H.J.; M aas, P.J.; Castelijns, A.M. J. Org. Chem., 1993, 58, 887 l.TMSCI,NaI,12 TMEDA , MeCN 2. NH3, loO°C 3. racemization-resolu tiono-II& K.L; Keller, J.L.; Purick, R.M Hartner Jr., F.W.; Choi, W.-B.; Askin, D.; Volantei R.P. Tetrahedron Mt., 1994, 35, 32i9 lTsHN Pd(OAc)z , EtzNH latmCO,THF,-TsCH2Ch. Andersson. PeGI; Aranyos, A. Tetrahedron Lxtt., 1994, 35,444;/ I q14) 72%Me -7OOC + -2OOCI Nt PhOZnCl OMeMe058%Me van Maanen, H.L.; Kleijn, H.; Jastrezebski, T.B.H.; van Koten. G, Reel. Trav. Chim. Pays-Bas, 1994, 113, 567Section 344Amide – Ester289BnNH2,10%NHTsYb(OT&CH2C12, rt, 1OhNHBnANHBn‘arts(>99 : 1) Meguro, M.; Asao, N.; Yamamoto, Y. Tetrahedron L&t., 1994, 35, 7395CL Nt-BUN& , NEt30%75%78%CH2C12, reflux , Id I Cl NHt-Bu Chen, P.; Suh, D.-J.; Smith. M.B, J. Chem. Sm., Perkin Trans. I., 1995, 1317 LSECTION 344: AMIDE – ESTER t-BuBr , KgO3, DMAC BTEAC ,55OC * Boc92%BocH DMAC = dimethyl acetamide BTEAC = BuEt3NCl Chevallet, P.; Garroust, P.; Malawska, B.; Martinez. J. Tetrahedron L&t., 1993, 34, 7409Mn(OAc)3 , CH$O2Me)2Chuang. C-P,; Wang, S.-F. Tetrahedron Lett., 1994, 35, 1283a;Lee, S.J. Tetrahedron Lett., 1994, 35, 1875290Section 345Compendiumof Organic Synthetic Methods, VoI91.15% ZnCl2 CH2C12 2. CAN, M&N, COPhPh Chen, T.; Jiang, S.; mos. E, Tetrahedron Lett., 1994, 35, 8325ClCO2Me Bu3SnH , AIBN , PhH *‘h0N’BnPh “i( 0N I Bn2:C&MePh 052% Goodall, IL; Parsons.A.F, J. Chem. Sot., Perkin Trans. I., 1994, 3257 01. Sn(OTf)z CHz,ClzC02MeN– Et2.**c-lOEtCOzMeC02Et‘;JCO,Et78% Nagasaki; Nishida, S.; Sugihara,S.; Kawahara,T.; Adachi, K.; Hamaguchi,F. ~etero~c~s, 1994, 39, 171 Section315 (Carboxylic Acid – Amide) Section316 (C~~xy~ic Acid – line) Section 351 (Amine – Ester)RelatedMethods:SECTION345: AMIDE- ETHER,EPOXIDE,THIOETHER OHCO/H2 (1600 psi) ,loO*C HC(OEt)3,24h H~(CO)(PPh)3 OSiMe342% OEt(2: 1 syn:anti)Eguchi, M.; Zeng, Q.; Korda, A.; Qiioma. I, Tetrahedron Lett., 1993, 34, 915291Amide – EtherSection 3451.P-O HPh PhJ3H3,TNF2. H+ , EtOH Bn Romagnoli, R.; Roos, E.C.; Hiemstra. H,; Mollenaar, M.H.; Sneckamp,W.N.; Kaptein, B.; Schafer, H.E. Tetrahedron Lett., 1994, 35, 1087ArAr = 4-nitrophenyl; Ar’ = 4-t-butylphenyl95% (66% ee) Hayashi, M.; Ono, K.; Hoshimi, H.; Qgni. N, J. Chem. Sot. Chem, Commun., 1994, 2699cyclohexanone, H$X&CN AcOH , Ac20, 10°C , Ih a&. J.-F,; Jung, L.; Hug, R. Heterocycles, 1994, 38, 297cat. ZnC12, CH2C12,50°C16d ~y~e~icPummerer rearrangement; Shibata,N.; Kawano, N.; Tohjo, T.; Fujimori, C.; Matsumoto, K. Tetrahedron Lett., 1995, 36, 115Section 346Compendiumof Organic Synthetic Methods, [email protected], C.J.; Spetseris,N.; NortonSECTION 346: AMIDE – HALIDE, SULFONATECl * l-L?ClClCuCl , cat. bipy98%I BnNagashima,H.; Ozaki, N.; Ishii, M.; Seki, K.; Washiyama,M.; Itoh, K. J. Org. Chem., 1993, 58,464Et3N*3 HF , MeCN77%t e”Narizulca, S.; Fuchierami. T, J. Org. Chem., 1993, 58, 4200IPPh#e(OH)OAc , I2 hv ,6Sh ;)76% Dorta, R.L.; Francisco, C.G.; Suarez. IE,~etr~he~~~~ Lett., 1994, 35, 1083NPh2w ~h/L; m1. b-AnP(S)S]z, PhMe , lOO*C 2. Bum2F3, NIS , CH2C12 o”c -+ l-t T, ~etr~he~~u~ Lett., 1994, 35, 3983F w wNPh2 98×64%Section 347Amide – Ketone293C3H70 b Nt-7VC, 6h BC120Meind Jt-1) 80% o. G,; Di Martino, E.; Gentilucci, L.; Tomasini. C,; Tomioni, L. Tetrahedron Asymmetry, 1995, 6, 1957 (>99SECTION 347: AMIDE – KETONE2DMP,4Py,lh CH2Clz, rtDess-Martinti0 NperiodinanePh75%Ph,hyr DMP = 1,1,l-triacetoxy-l,l’-dihydro-l,2-benzodoxol-3(1H)-one Batchelor, M.J.; Gillespie, R.J.; Golw. J.M.C,; Hedgecock,C.J.R.Tetrahedron Lett., 1993, 34, 16730% H202, Pd(OAc);! CH2C12,rt ,2h -73% *Naota, T.; Sasao,S.; Tanaka,K.; Yamamoto,H.; Murahashl.. 4843ii Tetrahedron Lett., 1993, 34,OEt0 TFA , 20°C, Id NNT -* 0 Br 0 J.-P*;Jacquesy,J.-C.; R~nbaud, D. Tetrahedrons 1993, 49, 223947%Section 347Compendium of Organic Synthetic Methods, Vol9294Bu$nH, AIBN, PhH (syringe pump addition) a 91%Beckwith. A.L,J,; Joseph, S.P.; Mayadunne, R.T.A. J. Org. Chem., 1993, 58, 41981. 3 Mn(OAc)3 2. H30+h /cossy. J,; Bouzide, A.; Leblanc, C. Synleft, 1993, 202 OTMS Me$iOTfNMeC02Mk, NEt3NMeC02MeO°C , lh Rossi, L.; J?ecumo. OMeA, Tetrahedron Lett., 1994, 35, 5285)IHewawasm3.12N HCl-DME , reflux /Me 01. BuLi, THF, O°C 2. (C02Et)2 I b85% I fi0 /NHCOzt-Bu P,; Meanwell, N.A. Tetrahedron Lett., 1994, 35, 7303PhCH=NC02Et,BF3eOEt2CH2C12, rt ,2d ten Hoeve, W.; Wynberg, H. Synth. Commun., 1994, 24, 899N H80x88%section 347Amide – Ketone295Me I1. Me~OHPh0 N-Me2.60% via heteroCope 3, Hz0 Lantos, I.; Zhang, W.-Y. Te~$~~e~r~~ L&t., 1994, 35, 5977 0OMe Si(iPr) 31. RCOCl 2. MeMgX 3. oxalic acid 4. TFA , CHC13, heat + ,yyi+* ,* i) NI 78~86% I CO2RR = (-)m8-phenylmen~yl Comins. D.L,; LaMunyon, D.H. Tetrahedron Lett., 1994, 35, 73431. t-BuLi , TMEDA , -78OC NiPr2t 2.Brenstrum, T.J.; Brimble. M.A,; Stevenson,R.J. Tetrahedron, 1994, 50, 4897 0NHAc I /I phi 0CoCl2, MeCN, AcClBhatia, B.; Reddy, M.M.; Iqbal. J, J. Chem. Sot. Chem. Commun., 1994, 713 bNfIMe4 eq. DMAP , toluene , refluxMec0ssv.z.; Belotti, D.; Bouzide, A.; Thelland, A. Bull. Sot. Chim. Fr., 1994, 131, 723NO2Section 349Compendium of Organic Synthetic Methods, Vol92%* 0”l.e-,AcOH,heat 2. MeOH, NazCO375x95% N N I I C02Me C02Me Matsumura. Y.; Takeshima, Y.-i.; Okita, H. BUZZ.Chem. Sot. Jpn., 1994, 67, 304iPrCH0, AcCl ,02, CoC12 = Reddy, M.M.;MeCN Bhatia, B.; -1.76%J, Tetrahedron Lett., 1995, 36,48770 cat. [Rh2(OAc)4] B-‘&/2=: = z59%Ge Podlech, J.; Seebach. D, Helv. Chim. Acta, 1995, 78, 1238SECTION 348: AMIDE – NITRILE 00 CNIIZN JLPhCNDMSO, O2 Ph88% Jain, R.; Roschangar, F.; Ciufolini. M.A, Tetrahedron Lett., 1995, 36, 3307SECTION 349: AMIDE – ALKENE.. (6 Khiar. NJ Femandez, I.; Alcudia, F. Tetrahedron L&t., 1993, 34, 11178%297Amide – AlkeneSection 3491. LDA , THF , -78OC ApcPh92%PhR 2. PhCHO , THF Ph I /q II I ph reflux Me Me 0 ; Deniau, E.; Grandclaudon,P. ~~tr~h~~ron Lett., 1993, 34, 14790 /lm%z, MS481, CH2C1220% chiral Yb triflate , O°C~~ .I(lobavashl.;(89: 1 en.do:exo; 95%ee) Hachiya, I.; Ishitani, H.; Araki, M. tetrahedron Lett., 1993, 34, 45354% Pdz(dba)3eCHC13 9.6% RS-BPPFOH silver~xch~ged zeofite c ~~ ~D~:DMSO0 (1Tetrahedron ktt.,Nukui, S.; Sodeoka,M.;Bf R -dFoEt, WC, 5d*.1.4) 94% (86%ee)1993, 34,4965, PPh3 /n-IFPhf14$.?Ph2% Pdz(dba)3~HCl3 2 eq. iPr2NEtOEtN 73%Bn Torii. &; Okumo~, H.; Sacked M.; Hai, A.K.M.A.; Tanaka, H. tetrahedron Lett., 1993, 34, 65530 I) -20”C, 36hPhb&imine*cu(OTE)2 (>97:3 en.do:exo) 72% Evans. D,A,; Lectka, T.; Miller, S.J. Tetrahedron Mt., 1993, 34, 7027298Section 349Compendium of Organic Synthetic Methods, Vol91.. 0.2 eq.fe(acac)s 3 eq. EtjAI/Lo+2. ethylene glycol cat. p-TsOH cc BzOws.m;Weidner, J.J.; Takacs, B.E. Tetrahedron Mt., 1993, 34, 62190.02 PdC12,2 eq. CuCL2 3 eq. ClCH,CQ-Na+ NHTs 9(C02MeCO. MeOHN53%Ts0 Kimura, M.; Saeki, N.; Uchida, S.; Harayama, H.; Tanaka, S.; Fugami, K.; Iama~~ Y, Tetrahedron Lett., 1993, 34, 7611 1. Et02C-N=N-COzEt , SnC4 CH2C12, -60°C, 5 min2 N-J-N*mC02Et2. Li , NH3 , -33°C 3.10 N HCl Brimble, M.A.; -cock.CL87 x 86% (1l:lE:Z)J. Org. Chem., 1993, 58, 5261Br Pd(OAc)z , P(o-ToI) , DMF Na$ZOs, BUflCl ,65”C, 40h sealed tube (in vacua) 4iEs+1) (4 Harris Jr., G.D.; Herr, R.J.; Weinreb. S.M, J. Org. Chem., 1993, 58; 5452 l78%Amide – AlkeneSection 349299Pd(PPh3)4,PhMe ,lOO°C Trost. B.M; Marrs, C.M. J. Am. Chem. Sot., 1993, 115, 6636 COzBn Ph$‘=CHCO2Et *80%toluene , reflux ,4hEt0 ~ Ba: 0 BOC Baldwin. JE,; Edwards, A.J.; Farthing, C.N.; Russell, A.T. Sy~lett, 1993, 49 CO2Me1. NaH , THF , BuLi CO2Me Ts>96% (>20:1 E=z)3. toluene , Amberlyst 15 , reflux &pB, Sy~~ett, 1993, 764 Ph PhCH2m2EtPh1.2 eq. LDA 2. Ph~H=NPhPhHN 758% 0 this reaction forms a p-lactamwith 1 eq. of LDA Manhas. M.S; Chaudhary, A.G.; Raju, VS.; Robbi, E.W.; Bose, AK. HeterocycZes, 1993, 35, 6351. xylenes , reflux 2. PPTS NaH , DMF THPO’ De la Torre, J.A.; Femandez,M.; mJr.. Tetrahedron Lett., 1994, 35, 1560% 68~75% D,; Smith, D.B.; Talamas,F.X.; Trejo, A.OMe Zn,THF,rt,lh NHCaMe Kise. N,; Yamazaki, H,; Mabuchi, T.; Shono, T. Tetra~e~r~~ Lett., 1994, 35, 1561300Section 349Compendiumof Organic Synthetic Methods, Vol979% W,; Fiirstner, A. Helv. Chim. Actu, 1993, 76, 2329Qpolzer.1. piperidine , [email protected] –YSPhTHF’rt 2. [email protected] NiCl,(dppe)* csH1& , THF , 0°C + rt 57×60%B&u&-i, F.; Fiandanese.V,; Naso, F.; Punzi, A. Tetrahedron Lett., 1994, 3.5, 20676 i/PhMe2CCH=Mo-N[2,6-(iPr)2C6H13] [ocMe(CF3)[email protected],rt80-90%n. S.F,; Liao, Y.; Chen, H.-J.; Patzel, M.; Ramser,M.N. Tetrahedron Lett., 1994, 35,&‘Ph3SO2PhBurley, I.; Hewson. A.T, Tetrahedron Lett., 1994, 35, 7099COzt-BuC02t-B u 52% (9O:lO E:Z)Wei, Z.Y.; m.EL Synlett, 1994, 345Section 349Amide – Alkene3010 ==cIl N, MS 4A, CHg12altoN CA/ N20% Yb-BINOL complex 7c-J== 0Me.t(8911) 77%95% ee Ishitani, H.; Araki, M.; Hachiya, I. Tetrahedron Lett., 1994, 35, 6325WS.;C02Et NH21. C02EtMe”“’ rl Ph, BF3GEt2, PhH , reflux2. [email protected],TI-IF , reflux+Jz+If2Me”““’ri PhH 76% (97:3)Barta, N.S.; Brode, A.; Stille. J.R,J. Am. Chem. Sot., 1994, 116, 6201 Ar NH2H2C0, [Rh(OAc)d2, PPh3, PhH -Iso 0N I 40% H Campi, E.M.; Chong, J.M.; Jackson. W.R,; Van Der Schoot, M. Tetrahedron, 2994, 50, 2533 AraI/ NHTsTs CsI-I17–CH=C=CH2 Ag3P04, 5% Pd(OAc)z/ w-h7his-oxazoline catalyst 90°C, Id, DMF 94% (82% ee)Larock. RC,; Zenner, J.M. .I. Org. Chem., 1995, 60, 482302Compendium of Organic Synthetic Methods, Vol9Section 349Ph-N=C=O , AlC13 ,4O”C Men&MetiNHPhMe 9CH2C12, 12h 0 Niestroi. M,; Neumann, W.P.; Thies, 0. Chem. Ber., 1994, 127, 113150% (4.9:1 E:Z)BQNF ,66OCBn Jacobi. P.A,; Brielmann, H.L.; Hauck, S.I. Tetrahedron L&t., 1995, 36, 1193 Bu 5% C12Pd(PPh&, MeOH, 65OC *CO (1 atm) ,4 NEt3AcAB’ci,N I AC78%Coperet, C.; Sugihara, T.; Nenishi. E, Tetrahedron L&t., 1995, 36, 1771 phwTePhTsNNaCl , EtOH ,20h 25OCNishibayashi, Y .; Srivastava, SK.; Ohe, K.; Ueuc),-‘“‘f‘+PhyNHTsOH 9% 84% Tetrahedron Lett., 1995, 36, 67251. LiHMDS , THF , HMPA , -78OC 2. PhNTf2, -78OC + 25OCclN o 3. PhguLi , THF-HMPA I -78OC + 25OC Bz Tsushima, K.; Hirade, T.; Hasegawa, H.; Murai. A, Chem. Lett., 1995, H Me+,,,,I 9(Me 0.1 AgNCO , 0.1 NEt3 , PhH 50°C, 5h NHTsN I Bz 80194×69% Ph-w/r”“’ N-Ts-lf0 0 Kimura, M.; Tanaka, S.; Tamaru, Y kBull. Chem. Sot. Jpn., 1995, 68, 168998%Section 350Amine – Amine303Also via Alkenyl Acids: Section 322 (Carboxylic Acid -Alkene)SECTION 350: AMINE – AMINE In , aq. EtOH , 16h ) NH&lN /Ph PhJPh Ph NHPh quant.NHPh Kalvanam. N,; Rao, G.V. Tetrahedron Lett., 1993, 34, 1647Plaquevent. J.-C,; Chichaoui, I. Tetrahedron Lett., 1993, 34, 5287 NHPhCN Hquant.* G+ Ph Rousselet, G.; Candevielle, P,; Maumy, M. Tetrahedron Lett., 1993, 34, 6395NHEt2 ,0.8 GPa , CH2C12 ,2d MeOH, 50°C 68% H Matsumoto. K,; Uchida, T.; Hashimoto, S.; Yonezawa, Y.; Iida, H.; Kakehi, A.; Otani, S. Heterocycles, 1993, 36, 2215Br1. t-BuLi , -78OC , THF 2.ZnC12 3. PdC12(PPh3h , Dibal THF , reflux * wSiMeg-BuBr Ior) 4. TsOH , EtOH Amat, M.; Hadida, S.; Bosch., J. Tetrahedron Lett., 1994, 35, 79393%N SiMe$-BuCompendiumof Organic Synthetic Methods, Vo19304AI,KOH,MeOH,rt,lOmin 2 ph-Section 351PhPhNPhPhHN Baruah, B.; ~ajapa~, ID.; mu.NHPh90% (70:30 dlmeso) J& Tetrahedron Lett., 1995, 36,6747(95 N&Nh. OH Ar = 4-OMe phenyl Shimizu, M.; Kami, M.; EU,jisawa.T, Tetrahedron Lett., 1995, 36, 86075) 71%SECTION 351: AMINE – ESTER1.COzEt ~echoech~;COzEtI”2, SmI2, THF ,25OC 70%Fem~~dez-Acebes, A. Tetr~~dro~ Lett., f993,34,549 Ph N I1. ImzCO , BF3*OEt2PhHN84%c( 7TMSAgF , EtOAc >MeCN , rt 15 min TM:(17 m.COzMe‘tTHF , heat Y 2. NaOMe , MeOII/THF 94% ph S,; D&u, M.D.; CarkSn,R.P. Tetrahedron Lett., 1993, 34, 725 PhAm.N-H(7:3 de) G; Lakshmaiah,G. Tetrahedron Lett., 1993,34,4861..SC ss, C02Et 3)98%Section 351305Amine – EsterI P1., BEt3, DMSO C02Et54%Fe2(SO)3~H20, hexane. Me ch;L,E;,Muraglia, E. Te~rah~dru~ Let?., 1993, 34, 5015 Ph PhOMe78:22 (anti:syn) * dried under microwave condi~ons Texier-Boullet. F,; Latouche, R.; Hamelin, J. Tetrahedron Let?., 1993, 34, 2123m. .P,; Pastor,A.; Vilaplana, M.J. Tetrahedron Lett., 1993, 34, 37731. Na+ NHS02Tol,60°C THF/DMSO, 19h ) M~~Npha~ -0Ac 2.03, NaOH/MeOH -78OC, 3h Jumnah, R.; Williams. J.M.J, Tetrahedron L&t., 1993, 34, 661990%) Et2N+ +‘“‘, )PhOqwt22. PhOH , NaOH , THF C8h7C8h761% 30% Richardson, P.F.; Nelson, L.T.J.; Shamless.K.B. Tetrahedron Lett., 1995, 36, 924117hv , PhSH ,2hfl..(826:12) 66%trans:cis Naito. T,; Honda,Y.; Miyata, 0.; Ninomiya, I. J. Chem. Sot., Perkin Trans. l., 1995, 19SECTION 353: AMINE – HALIDE, SULFONATE Br2, CH2C12 0.5 MeOH * 0.01 Et3NHClBrr-(=)-NMe2 near quant.Gervat, S.; Lbnel, E.; Barraud,J-Y.; Ratovelomanana. V, Tetrahedron Lett., 1993, 34, 2115 “Ni;?B” , H20,15OC ,30 min 72% “Ni2B” = Ni(OAc)2.4 HzO/NaBHd Seltzman. H.H,; Berrang, B.D. Tetrahedron Lett., 1993, 34, 3083312Compendium of Organic Synthetic Methods, Vol9Section 354CF3SiMe3 , THF Etw, 15h,rtFelix, C.P.; Khatimi, N.; Laurent.Tetrahedron Lett., 1994, 35, 3303mco2Et 0iPrOH,HCl(+rt+ CNI HFoley. L.H, Tetrahedron Lett., 1994, 35, 598996%SECTION 354: AMINE – KETONEC Rechsteiner, B.; Texier-Boullet,+ ON Imicrowave (300W) 3 minUPh 0I /, SiO2N-HF.; j-bnelin.O- Li+0 TfO–78OC89%J, Tetrahedron Lett., 1993, 34, 5071/rHF*35%23OCF . Kiselyov, A.S.; &&QWS~ I,, J. Org. Chem., 1993, 58, 4476hv ,9,10-dicyanoanthraceneZhang, X.; Jung, Y.S.; -0. 1993, 34, 5239P.S.: Fox. MA;78% Martin, P.S.; Merkert, J. Tetrahedron Lett.,Section 354Amine – Ketone313hv*Winkler. JD,; Siegel, M.G. Tetrahedron Lett., 1993, 34, 7697Mehv ,9,10dicyanoanthracene MeOH/MeCN,,o*,MeM fd ,\-BnNBn 23% at 73% conversionTM .Khim, SK.; Marianr,. PLS, Tetrahedron Lett., 1994, 35, 999PhNH;! , PhH , reflux-*N I Ph90% Adembri. G,; Celli, A.M.; Lampariello, L.R.; Scotton, M.; Sega, A. Tetrahedron L&t., 1994, 35,4023 CT NH21. PhCHO 2. TMSOTf , MeCN acetophenone&q- THF , -78OCWegman, S.; Wiirthwein. E.U. Tetrahedron Lett., 1993, 34, 30;0 NPhCHOcat. PdC12(PPh3)2 MeK2C03I (E+Z)Ph in Toluene 10% 85% in DMF 72% 2% Filionini. L,; Gusmeroli, M.; Riva, R. Tetrahedron Lett., 1993, 34, 1643 0OBu1. LDA , -78°C THF + xylene2. xylene , reflux ,4h b,tiHBumoda.&HBu(99.5 : 0.5) 92% T,; Tats&i, S.; Shiraishi, Y.; Akasaka, M.; It& S. Tetrahedron L&t., 1993, 34, 3297 OMe OMe1. BF3aEt2, 2. crc12THF3. ally1 bromide , rt P4. 10% aq. Na2C03Giammaruco, M.; Taddei. M,; Ulivi, P. Tetrahedron Lett., 1993, 34, 363565%Section 356Amine – [email protected]‘t-1. PPh3%@EtC02EtEt02C02Etam-EtO$92%Palacios.F,; Perezde Heredia, I.; RubiaIes,G. Tetrahedron Lett., 1993, 34,4377. -K.;Kaneko, M.; Yajima, T. Tetrahedron L&t., 1993, 34, 4841 hBu$nH , AIBN ,O.O5M (syringe pump) ,2hNHPhh +piPAPhvvSePh45%23% Refvik, M.D. Tetrahedron Lett., 1993, 34,490lSchvvan.;Me$ (CH20)n, p-tsOHaH20 MeCN ,6Q*C67-69% (64-67%ee) 4’J4Hb,,*,BnBnH Castro, P.; OvemJ&;Zhang, X.; &briano, P.S, Tetrahedron Lett., 1993, 34, 5243 t-BuNH2, MS 3A, 2h CH2C12,22*CMerrr,,, t-B94%Sigman, M.S.; Eaton. B.E, Tetrahedron Lett., 1993, 34, 5367t-Bu H318Compendium of Organic Synthetic Methods, Vol9Section 356Pbl.LDA.THF78% de1 Pozo Losada, C.; Olano, B. Tetrahedron Lett., 1993,34, 5497Barluenu;Bi/BuflBr, MeCNPON-Pb -BrBbuyan, P.J.; Prajapati, D.; Sandhu, JS, Tetrahedron Lett., 1993, 34, 7975N Cb, toluene , bv ICH20Et2.23OC, 12b 3. TBAFN cd N CH20Et91%Knapp. S,; Albaneze, J.; Schwar, H.J,J. Org. Chem., 1993, 58, 997(66..34)I BnPbBebolz, L.G.; Stille, J,R, J. Org. Chem., 1993, 58, 5095 Phi , Pd(PPh& K2CO3 DMF , 70°C NHBn Davies, I.W.; Scopes, D.I.C.; Gallagher, T. Synlett, 1993, 8599%Section 356Amine – Alkene319SnBu3 Bn.I;;IJJTYyHBn+p-Me. (17 Coldham. I, J. Chem. Sot., Perkin Trans. I., 1993, 127583) 65%Leurs, S.; Vanderbulcke-Coyette,B.; Viehe, H.G. Bull. Sot. Chim. Be&., 1993, 102, 645V9:nzBr3NHPhDMFPhLJin, S.-J.; Araki, S.; Butsunan. Y. Bull. Chem. Sot. Jpn., 1993, 66, 1528SEtBn Aw HAlC13, CH&, rtvoms NHBnOTBS84%SEtr 77% Tohyama, Y.; Tanino, K.; Kuwajima. I, J. Org. Chem., 1994, 59, 518 I4 wNHTsBr ’5% Pd(OAc);!N 10%P(o-Tol)3 , Na2CQ I -Ko Ts 88% 2 [email protected] ,9O”C, Id Larock. RC,; Yang, H.; Weinreb. S.M,; Herr, R.J. J. Org. Chem., 1994, 59, 4172320Com~n~umof Organic Synthetic Methods, Vo19Bernard-Henriet, C.; Grimaldi, J.R.; Hatem.Section 356NHNMe2 89% Tetrahedron Mt., 1994, 35, 3699N I..(2.7 pearsOn. W&;Me 1) 65%Jacobs, V.A. Tetrahedron Lett., 1994, 35, 7001 PhNHOl-l , FeC12/FeC13 72% *Srivastava, R.S.; Nicholas,.M.NHPhtetrahedron Lett., 1994, 35, 8739dco2t-BuC7HlLDA Ahman, J.; &&&j.P,J, Am. Chem. Sot., 1994, 116, 9781Ph-NW1. Ni(cod);! , MeCN Br45% 2.16 NaBH4,6 MeOHSol& D.; Cancho, Y.; Llebaria, A.; Moret6, J.M.; Del&ado. A, J. Am. Chem. Sot., 1994, 116, 12133Amine – AlkeneSection 3563211% (PCy3)g12Ru=CHCH=CPh2 wPhH , eflux ,6h a &I 86%‘OAc Kinoshita, A.; Mori. Synlett, 1994, 1020 – OAc –C-JO Fisher. GB,; Lee, L.; Klettke, F.W. Synth. Commun., 1994, 24, 1541 Ph Zn(Cu) , MeOH, H20, rt /Ne . m.Brultrasound&, Jolie, R.; De Smaele,D. J. Chem. SE Chem. Cajun.,1994,53% 1221Ph C02t-BufNLDA , TI-F , -78OC -n-N I HC02t-Bu63% Coldham. I.; Collis, A.J.; MouId, R.J.; Rathmell, R.E. Tetrahedron Lett., 1995, 36, 3557Et2N HNEt2, 20% Et3NHI, THF 10%Pd(dba)z,2 PPh3 65OC,c7-h18hC7Hti J 70% (96:4 E.-z)Besson,L.; Go&, J.; Gazes.Tetrahedron Lett., 1995, 36, 3857322Compendiumof Organic Synthetic Methods, Vol9Section [email protected] TfNaCH(C02Me)2,5% Pd(PPh& LiCl , DMSO , 60°CC02Me *N Bn’Vieart, N.: Gazes,B.; m C3H7jBnA v53%Bn’ Tetra~dronLett., 1995, 36, 50 15ether, -5OOC-+ -1OOC,4hPhF== C3H7PhPhProi/TiOiPrGao, Y.; Harada,K.; Usato, F. Tetrahedron Lett., 1995, 36, 5913 Ph Bu+i’–@ *phi15% Yb(OTf), , CH$12, rt N HN Ph Ph Bellucci, C.; Cozzi, P.G&;Umani-Ronchi, A, Tetrahedron Lett., 1995, 36, 7289 1. ~~~~~~ ph-NPhNHPh, Me$iCl2. [email protected] 96%Wang, D.-K.; Dai. L.-X.: Hou. X.-L, Tetrahedron L&t., 1995, 36, 8649 Ph2PPh2PIPh w–h3w-h3(8cc;&3 l .1) 80%(5:1 cis: tranws)Didiuk, M.T.; Morken, J.P.; fioveysla. A& J. Am. Chem. Sot., 1995, I1 7, 727356%Ester- EsterSection 35732313F3*OEt2, 210°C ,2h wBr Ph~5 eq m~~huline , lOO*C 10 eq. H20, 2dSECTION 357: ESTER – ESTER~~~~H f AIBN , TuI reflux ,2h0 Ph ; Kee, I.S. Te?~~~e~~~~Lett., 1993, 34,42132. Hfl 3. p-TsOH , tolueneShimada, S.; Tohno, I.; Hashimoto, Y.;*. 8) 85~ (92 Chem. Lett., 1993, 1117324Section 357Compendium of Organic Synthetic Methods, Vol9l/50 CoC12 ,42h *OHOCHODME , 02, 80°CLi, P.; Alter.H, Can. J. Chem., 1993, 0 C02Meacetone, SmI2 , THF 4% Fe(dbm)3 , refluxC02Me 74%CO2Me-b Imamoto. T,; Hatajima, T.; Yoshizawa, T. Tetrahedron L&t., 1994, 3.5, 7805 Mf30OTMSI Pd(PPh3)4, TlOAc OMe , HF reflux , Id 89% T,; Kondo, Y.; Masumoto, K.; Yamanaka, H. J. Chem. Sot., Perkin Trans. l.,aoto. 1994,235PhCHO , Cp2Sn(thf)2 0-To1 , O°C + 25OCA(&()‘phTakano, M.; Kikuchi, S.; Morita, K.; Nishiyama, Y .; m.77% Y. J. Org. Chem., 1995, 60, 4974NaB0~4 [email protected] , Ac20, PhH Ph Nag03,55OC,14h 67%Bhat, S.; Ramesha, A.R.; Chandrasekaran. S, Synlett, 1995, 329 Also via Dicarboxylic Acids: Hydroxy-esters DiolsSection 312 (Carboxylic Acids – Carboxylic Acids) Section 327 (Alcohol – Ester) Section 323 (Alcohol – Alcohol)325Ester- Ethersection 358SECTION 358: ESTER – ETHER, EPOXIDE, THIOETHER Bu$W-I , AIBN sPhH reflux ,6h, syringe asp tLee.;Br Tae, J.S.; Lee, C.; Park, CM, T~tra~dr~n Lett., 1993, 34,4831 [email protected] CsF , M&N 2,Meo2 k92%C02MeHojo, M.; Ohkuma, M.; Ishibashi, N.;Tetrahedron Lett., 1993, 34, 5943 OTMS(Tf~)2Sn(bis~~ine) w CH2C12,9h , -78OCPhEtS IPhCHO86~ (93:7 ~~n:a~ti)Kobayashi, S.; IJchiro, H.; Shiina, I.; Mukaiyama, T. Tetrahedron, 1993, 49, 1761 OzEt1.3Bu$nH 0.25 AIBN C.X&Et 0.03M PhH reflux ,8h54) 91% (46 ; Tae, J.S.; Chong, Y.H.; Park, Y.C.; Yun, M.; Kim, S. T~tra~~dr~n Let& 1994, 35, l129CCHOems ===c,40% sno SEt20% Sn(OTf);! chiral diarnine slow addi~ou (3h) ; Kawasuji, T.; Mori, N. Chem. Let& 1994,217SEt 61% (62% ee)326Section 359Compendium of Organic Synthetic Methods, Vol9COZMe Rhz(OA& , MeOH49% Tet~a~d~~~ Lett., 1994, 35,Cox, C.G.; Haigh, D.; Hind~~y, R.M.; Miller, D.J.; 31390 CP “_/“e1. PhCHO , ZnC12 , CH2C12 , rt 2. CAN, MeOH, -78OC, CO= Me0 Phoc T~trahed~~~ Lett., 1994, 35, 7889Jiang, S.;~cl2-AgPF6, MeO$COzMeCH$&CO,n/leMeOHMeO$Zf==cC02Mequant. Kataoka, Y.; Ma~umot~, 0.; Ohashi, M.; Yamagata, T.; Tani. K, Chem Lett., 1994, 1283SECTION 359: ESTER – HALIDE, SULFONATE [CF2Br$Z#n, DMF ,2h, rt] HMPA , CuBr , 60°C, 40 min *98% 00 Mawson, S.D.; Weavers. R,T, Tetrahedron Let& 1993, 34, 3139HoqoH3HBb~~,lhh_Bc= S= r:=: == =$H&HXAcXAC2.2 MeCOBr , dioxane ) 16h80% El Anzi, A.; Benazza, M.; Frechou, C,; Demaillv, C, Tetrahedron Lett., 1993, 34, 3741BrEkter- HalideSection 359327CHzC12,18h m-cCO2Hhis-(sym-collidine) iodine(I) hex~~ophosphate Simonot, B.; Rousseau G, J. Org. Chem.,1993, 58,476% I89%Kitagawa, 0.; Inoue, T.; Hirano, K.; muchi.T, J. Org. Cbem.,1993, 58, 3106IQ, sodium persulfate, NaHC03 HOD Royer, AC.; Mebane, R.C.; Swafford, A.M. SynZett, 1993, 899BzCl ,0.4 SmI3, MeCN , rt tBzO/-IYu, Y.; m.87% Y,; Ling, R. Synth. Commun., 1993, 23, 1973*c1. HC=CC02H, NC1 , CH2C12 2. (BzO), , PhH, efluxHaaima,G.; Lunch, M.-J.; Routledge,A.; Wu78~44%Tetrahedron, 1993,49,[email protected], DMSO BEt3, rt (opento air)C02Et -; Mu~gl~, E. Tetr~~~~r~~ Left., 1994, 35, 276354%328Compendiumof Organic Synthetic Methods, Vol9BQ #y-CO2H1. mcpbaSection 359ONlb22.12, NaHC03 50%Reetz. MT,; Lauterbach,E.H. Heterocycles, 1993, 35, 627 Meb.X,; Wang, 2.; Ji, J. Tetrahedron Lett., 1994, 35, 613Mimero, P.; Saluzzo, C.; m.R, Tetrahedron Lett., 1996, 35, 1553BeIIesia, F.; Boni, M.; Ghelfi. F,; Pagnoni, U.M. Tetrahedron L&t., 1994, 35, 2961 FzBrBu$nH , AIBN, PhHt reflux , l-15 h addition ~ Meat ButtIe, L.A.; Motherwell. W.B, Tetrahedron Lett., 1994, 35, 3995 MeOgSection 359Ester – Halide3290 A Buoysmac1TBAB 190°C ) 6h S 97% K~ey~~A.; Kiyota, M.;Ph YT~tr~~~drun L&t., 1994, 35, 4571 ClAcCI , Cp2YCI w CH2C12, 13hAcO ~Ph..(88 ; Zhu, I), ~ynt~. ~~~~~.~ClACPh 12) 95%1994, 24, 2203I2 , Pb(OAc)za3 Hz0 , AcOH wrt ,6h 85% Bedekar, A.V.; Nair, K.B.; S~rn~n. R, ~ynt~. ~u~~~n., 1994,24, 2299 BrPhMe3Nf Brf Ir Br; G&in, R.H.; Musket,GM.; Aionso, M.S. Tetr~~edrun, 1994, 50, 6433ClPimmg, F.O.H.; 1994,50, 124150.3 Cu(~py)C~ , DCE57% (70:30) ; Kaptein, B.; Schoemaker, H.E. Tet~~~dr~~~Compendiumof Organic Synthetic Methods, Vol933000, Zn , ether0 w25OC, 18hClSection 360PhK,///c’ 70%Bhar, S.; &nu. BC, J. Org. Chem., 1995, 60, 745 SECTION360: ESTER – KETONE 0 55%1. BrOHKtrBr Py, ether Cd-f23 53% 2. TMSCl , ether cl lH23 Zn , reflux Landi Jr., J.J.; Garafalo, L.M.; &.mig. K, Tetrahedron Lett., 1993, 34, 277 COzMe2% Rh2[02CCH(Bn)NPhth]4 C02MeCO2Me CH2C12,O°Cd-3S S bh96%(46%ee, R) Hashimoto, S.; Watanabe,N.; Sato,T.; Shiro, M.; Ikegami. S, Tetrahedron Lett., 1993, 34,5109Ph1.7 PhI(OH)OTs , CDC13-A rt ,2h 98% CO2Et C02Et Barton, D.H.R.: Jaszberenyi.J.Cs,; Shinada,T. Tetrahedron Lett., 1993, 34, 7191 PhCHO , EtN02 AlC13, 100°C, 5hSartori. (i; Bigi, E.; Maggi, R.; Bemardi, G.L. Tetrahedron Lett., 1993, 34, 7339331Ester – Ketonesection 360BrPhLl-, csgo3,CH$& C02Et48h, 30°C 2. aq. HCI, CHCI3 , Him-da, Y.; unhip,;Tanaka, Y,; Ueda, I. J. Org. ~~~.,1994, 59, 1111. (Coa)2 , hv t60%2. MeOI-I02Me ; Hardee, J.R.; Gelber, N.; Qi, L.; Axenmd, T. J. Org. Cbem., 1994, 59, 2131ICI-I ) THF ,18-c-6 , rtMe60%ACPh JLOAc ,4% Pd(P~h3)2C12Clw C7Hl KSnBu3Ph C7Hl8% CuCN ,75”C, 18hJ, Am. Cam. Sot., 1994, 116, 1Ye, J.; Bhatt, R.K.;N c1Ph -IfCO&B uIsJr&o. B, Te&hedron96%L&t., 1994, 35, 507374%332Section 360Compendium of Organic Synthetic Methods, Vol9MeMeMn(OAc), , AcOH 8O”C, 8h wMe02CC02Me 57%C.-P,; Wang, S.-F. Tetrahedron Lett., 1994, 35, 4365 1, NaH , DME ,40°C 2. BuLi 3. PCC , Al203 , CHg12 93x68x68% Piers. E,; Cook, K.L.; Rogers, C. Tetrahedron Lett., 1994, 35, 8573 0 KMn04, CuSO&Hz0 47%4h * Das, J.; wS, Tetrahedron, 1994, 50, 11709 e- , CH2C12- Hz0 NaBBr2C02MeC02Me 87%Maekawa, H.; Ishino, Y.; mguchi. OH PhI-L Chem. L&t., 1994, 1017aq. t-B&OH, C02Et1% CuC12,3% TBABCH2C12, 25OC, IdPhAC02Et 96%Feldberg, L.; Sasson. Y, J. Chem. Sot. Chem. Commun., 1994, 1807Section 360Ester=Ketone33368% Ryu, 1; Nagahara,I(.; Yamazdci, H.; Tsunoi, S.; Sonoda. N, Synlett, 1994, 643Bu$nH, AIBN(9m,Kinter, KS. J. Org. Chem.,1995, 60, 4850 OCQMeBarba, I?.-e’ , DMF/LiCIOd67% h&G.: Montero. Cr..I. Org. Chem.,1995, 60, 5658 KMn04, pH 7 OEtTat‘iock. J,& J. org. Ckm, 1995,C02t-B u60,OEt 0 97%62211. CuBr2, PhI(OH)OTs , 0°C 2. DMAP .,dimethyldioxirane CH2C12,O”C0 [email protected] 01st stepis quant Coats, S.J.; Wasserman.H.H, Tetrahedron Lett., 1995, 36, 7735OPh1.J-I-IFLiPhCHO w;Section 361Com~n~um of Organic Synthetic Means, VoI 9334oAc88~78%2. p-TSA , A&H, 90°C , ld * PhA/ Yang, 2.; Moutou, J.-L. Tetrahedron Lett., 1995, 36, 841–c BrSmI2, THF , -35*C, 5 min4 072%d Park, H.S.; Lee, I.S.; I(im. YKTetrahedron Lett., 1995, 36, 1673REVIEW:“Alternate PreparationsOf aXeto EstersFrom Acid Chlorides,” &&i&&y. A,&; Wang, 2.; Wells, A.P. Org. Prep. Proceed. Int., 1995, 27, 457 AIso via ISetoacids HydroxyketonesSection320 (Carboxylic Acid – Ketone) Section330 (Alcohol – Ketone)SECTION 361: ESTER – NITRILE OAc I phwCHONc Pdz(dba)&HQ , dppe MeCN, IdNemoto, H.; Kubota, Y.; Yamamoto. Y cJ. Chem. Sot. Chem. Commun., 1994, 1665TBAF,THF,lh LiCI , rt94% CNStojanova, D.S.; Milenkov, B.; Hesse.M, Helv. Chim. Acta, 1993, 76, 2303Ester- AlkeneSection 362335ESTER – ALKENESECTION 362:This sectioncontains synthesesof enol estersand estersof unsaturatedacidsas well asester moleculesbearing a remotealkenyl unit. 0C02H1. Br2, NaHC03 2. AgNOj , AcOHBuBu 66×50%J&,&T&; Huang, J. Tetrahedron Lett., 1993, 34, 1411 1. &CO3 ,5 kbar 2.5% Pd(OAc)z , 10% P(2-furyl)3Jco2H61%3. HC=CCMe20Ac, DMSO 20°C , 14h ** Bouyssi, D.; Gore, J.; BaIme, G.; Louis, D.; Wallach, J. Tetrahedron L&t., 1993, 34, 3129 Me90% Ciattini, P.G.; Mastropietro, G.; Morera, E.; Ortar, G, Tetrahedron Lett., 1993, 34, 3763Ph-C=CH , NEt3, MeCN , rt 0 PdC12(PPh3)2 , CuI , 1OhCu. X,; Huang, X.; Ma, S. Tetrahedron Lett., 1993, 34, 5963Me$iCH=C=O , PhH OSiMe3reflux ,3dMe$iO Ito, T.; WT…. ..Me& T, Tetrahedron Lett., 1993, 34, 6583P Ph80% (>97:3 z:E)336Compendium of Organic Synthetic Methods, Vol9[email protected] 362PBn [email protected], 80°C65%OBn&lark& I.&; Evans, G.R. Tetrahedron tett., 1993, 34, 7309Co-Cl2 [email protected](30Me0 Et..70) 29% [60:40 E:zJBhatia, B.; Reddy, M.M.; [email protected] L&t., 1993, 34,630l1. SnC12 / 2.=c_ ut.CI-IO ,ether,rt >F,; Gabriel, A.; Maillard, B.; Pereyre, M. Tetrahedron Lett., 1993, 34, 7749 cww bock.5% Pd(OAc)z ,2 NaOAc DMSO , O2 )am086%RC,; Hightower, T.R. J. Org. Chem., 1993, 58, 5298 BnAcHN -A1. PhSeCH$H20H, cwWeinhouse, ML; Janda.EDCDMAP , DMF 2. [email protected], THF 3. iPr$H , CHCl3, reflux Synthesis, 1993, 8 1Bn w AcHN04 92×90%Section 362Ester – Alkene337+hcCO2HDMSO , Na2CO3 28-46h70% Tetrahedron L&t., 1993, 34, 8545Annby. U,; Stenkula, M.; -C.-M.30%;Jmco2EtPPh3 7PhH , rt ,8hGuo, C.; Lu..I. Chem. Sot. Chem. Commun., 1993, 394 Et0OMeCO2Me,O.S Bu$nH E tog-41% doMeLee. E,; Hur, CU.; I&e, 1466,0.05 AIBN , reflux ,4h PhH (0.01 M) , syringe* pump v(2h)C02Me Y.H.; Park, Y.C.; Kim, S.Y. .I. Chem. Sot. Chem. Commun., 1993,P(OEt)3 , NEtyH20,120OC -C02Et-COzEt8h (sealed tube) 96%Hirao. T,; HirawK.; Ohshiro. Y, Bull. Chem.TIN,SOC.Jpn., 1993, 66, 2781MeOH,3MHCl 3-26hMe0 Me0 Thakkar, K.; Cushman, M, Tetrahedron Lett., 1994, 35,644lSection 362Compendiumof Organic Synthetic Methods, Vol9338Pd(OAc)z , dppp , PhMe , MeOH w COzMe refluxMand;u. TJ Tsujiguchi, Y.; Tsuji, J.; Saito, S. Tetrahedron Lett., 1994, 35, 5701 Bu [Pd(MeCN)2(p&)d @=I12 co, THE;, 5o”c (10 Kg cms2)‘b O+Bux; 283) 92% Y, Tetrahedron Lett., ;994, 35, 5889(17Matsushita, K.; Komori, T.; Oi, S.; w.l.NaI-I,TMEDA,THF,reflux 2. inverse addition to PhOCOCl0aOPh 43%Harwood, L.M.; Houminer, Y.; Manage, A.; Seeman.J-1,Tetrahedron Lett., 1994, 35, 8027eC02Me PhCHOphL-oH34%DABCO , microwave, 10 min CO2Me Kundu, M.K.; Mulcherjee, S.B.; Balu, N.; Padmakumar,R.; I$&& S.V,Synlett, 1994,444 BrCHzCOfle , Bu3As , 10% Cd PhCHO100°C ,20hZheng, J.; ahen, Y, Synth. Commun., 1994, 24, 2069PhwC02Me 87% (E only)Nz)I339Ester – AlkeneSection 362Lf Rh2(s-TBSP)4CO2Mep-(t-butyl)phenylsulfonyl prolinate 76% (63% ee) . TBSP = Peng, ava; Z-Q.; Houser, J.H. Tetrahedron Lett., 1994, 35, 8939 Mac,3.5% Pd(OAc)z 8% PPh3 , 1.2 Ag2CQ , MeCN 90°C, 45 min 80%Meyer, F.E.; Ang, K.H.; Stenig, A.G.; de Meijere, A. Synlett, 1994, 191 -0Ac, CO, THF , autoclaveRuC12(PPh3)3-K2C03, 2OOOC, 77%Kondo, T.; Kodoi, K.; Mitsudo, T.-u.; Watanabe.Y t J. Chem. Sot. Chem. Comnun., 1994, 7551. Rieke Mg* , THF , rt 2. ethylene oxide ) THF , -78OC v3.co;!,o”c + rt 4. H30+, 1lOCRieke. R.D; Sell, MS.; Xiong, H. J. Org. Chem., 1995, 60, 5143 Me0nBu3 SPhcu(No3)2Ph9m 9fiCO2Me 65%TVCO2Me SPh Beddoes,R.L.; Cheeseright,T.; Wang, J.; Quayle. P, Tetrahedron Lett., 1995, 36, 283340Compendiumof Organic Synthetic Methods,Vo19Section 362COzMe Ph3ACO2MeSePhPhCHOCHC13,4h Huang, Z.-Z.; Huane,SePh Y. -7* Tetrahedron Lett., 1995, 36,425-F C3H796% (90:10, Z-E)PhHw7Ph5% ClzPd(PPh3h.4 NEt3 20atmC0,PhH,l10°C,10h99%Cop&et, C.; Sugihara, T.; Wu, G.; Shimoyama,I.; Negishi. E, J. Am. Chem. Sot., 1995, 117, 3422 -cl; NEI+;IH2C12,-20°Ca *w.OBn 75%G,; De Simone, A.; Mingardi, A.; Tomasini, C. Synlett, 1995, 11313) 95%(>97Zhu, G.; Lu. X, Tetrahedron Asymmetry, 1995, 6, 345 m PhOClSiMe3 , toluene AlC13, 20°C ,2hPhOL 82%Mayr. H,; Gabriel, A.O.; Schumacher,R. Liebigs Ann. Chem., 1995, 1583Section 363osMe3OPl. m.341Ether – EtherM+CCOzMezrC14,Cc4,0°cpflzc+ rtMew . &, Sudoh, T.; Koyama, K. Bull. Chem. Sot. J’n., 1995,68, 1683 RelatedMethods: Also via Acetylenic Esters: Alkenyl Acids: P-Hydroxy-esters:SECTION 363:80%Section60A (Protectionof Aldehydes). Section 180A (Protectionof Ketones). Section 306 (Alkyne – Ester). Section322 (Carboxylic Acid – Alkene). Section 327 (Alcohol – Ester).ETHER, EPOXIDE, THIOETHER EPOXIDE, THIOETHER- ETHER,SeeSection60A (Protectionof Aldehydes)and Section 180A (Protectionof Ketones)for reactionsinvolving formation of Acetalsand Ketals. 1. DDQ , MeOH , CH2C12 rt, Id 2. aq. NaHC03 OMe &I. Y.-C,; Lebeau,E.; Gillard, J.W.; Attardo, G. Tetrahedron L&t., 1993, 34, 38414 /iPrOH ,20% CuC12 5% Pd(N0)2C1(MeCN)2 2h50% isolated Meulemans,T.M.; Kiers, N.H.; FeringZLR.L; van Leeuwen, P.W.N.M. Tetrahedron L&t., 1994, 35, 455HODEAD, PPh3, CHg12, O°C HO OH80% @-only) Sobti, A.; Sulikowski. G.A, Tetrahedron L&t., 1994, 35, 366178%Section 364Compendiumof Organic Synthetic Methods, Vol9342(a$ = 1:15) 81% BTIB = his-(trifluoroacetoxy)idobenzene Sun, L.; Li, P.; Zhao. K, Tetrahedron Lett., 1994, 35, 7147 TMS-SPh , DMF w‘OMe ;w”lMiura, T.; w.87%Y, Tetrahedron Lett., 1994, 35, 7961 OSiMqt-Bu Q = 2 sOMeZnI2 , THFp-To170% (>99% e) Kita. Y,; Shibata, N.; Fukui, S.; Fujita, S. Tetrahedron Lett., 1994, 3.5, 9733ETHER, EPOXIDE, THIOETHER SULFONATESECTION 364:1. ClCH21, MeLi , -78°C ‘Ls 2. -78OC ++20°cBr Barluenu;- HALIDE,Me4N*#,,,, ,,+,Me 62% $ClLlavona, L.; Bemad, P.L.; Concellbn, J.M. Tetrahedron Lett., 1993, 34, 3173 HXeF2, CH2C12,35OCStavber, S.; Zupan, M. Tetrahedron Lett., 1993, 34,4355Section 364Ether – Halide343MnO2, AcCl w Cl 82% Bellesia, F.; Ghelfi, F.; Pagnoni, U.M.; Pinetti. A, GQzz.Chim. Ital., 1993, 123, 289t(OMeOMeBr2, Me&Cl, NaBr ,30 min B *OMe3-(OMe 98%Bell&a, F.; Boni, M.; Ghelfi.;Pagnoni, U.M. Gazz. Chim. Ital., 1993, 123, 62960% Antonioletti, R.; Magnanti, S.; Screttri, A. Tetrahedron Lett., 1994, 35, 2619 l.LDA,HMPA 2. acetone 3. X2,NaHC0332x47% Galatsis. P,; Parks,D.J. Tetrahedron L&t., 1994, 35, 6611 H ,,OH @9,,\I”l12, NaHC03 , dry MeCNIIIIIIIIB uBu 16h 04d-Jr,e % -175% Barks, J.M.; Knight. D.W,; Weingarten, G.G. J. Chem. Sot. Chem. Commun., 1994, 719 PhI(&~F3)29t t 12 cc14D’Auria, M.; Mauriello, G. Tetrahedron Lett., 1995, 36,488383% ISection 365Compendiumof Organic Synthetic Methods, Vol9344AK13 , Id(4 s1) 60%J.0,; Biermann, U. Bull. Sot. Chim. Be&., 1994, 10, 393CT I(collidine)$ PFi tA//CH2Cl295%Brunel, Y .; Rousseau,G. Synlett, 1995, 32312, CAN, MeOH *rt ,2hI*I1) 88% (2 6 ; Hosokawa,H.; Kanamori, M.; Muramatsu, Y.; bhiai, K.; Takahashi,E. Chem. Lett., 1995, 13 .SECTION365:ETHER,EPOXIDE,THIOETHER- KETONE Me‘OSiMe3OHBFpOEt2, MeN02, -25OC 30 min?Y-51%(7:3 syn:anti)Duhamel. P,; Guillemont, J.; Poirier, J.-M. Tetrahedron Lett., 1993, 34, 4197 2% Cu(hfacac)z, CH2C12 40%reflux *hfacac = hexafluoroacetyl acetonate Clark. J.S; Krowiak, S.A.; Street,L.J. Tetrahedron Lett., 1993, 34,4385Section 365Ether – Ketone3452Me:3Me) II 0M&, Rivera-Fortin, M.A.; Byrne, N.E. Tetrahedron Lett., 1993, 34, 3505 Ph, t-Bu, Me2AIClA-,,,,,d PhSPhCH2C12,-45OC(96:4) where 4 = other isomers Horiguchi, Y.; Suehiro, I.; Sasaki,A.; Kuwaiima, I, Tetrahedron Lett., 1993, 34, 6077 Me MeTMS zcI cf5% TMSN(S02F)2 CH2C12,-78OCTrehan, A.; Vij, A.; Walia, M.; Kaur, G.; Veu.. 7335p-TsOH , H20, CH& 20°C, 12h Cossy. J,; Furet, N. Tetrahedron Lett., 1993, 34, 7755&r. Treh;iB. S, Tetrahedron Lett., 1993, 34,SePh 70%346Section 365Compendiumof Organic Synthetic Methods, Vol9[mCl(C2H4)d2 9 SnC12acetone, Ar , 80°Csealedtube, 1Oh-* Tetrahedron Let?., 1993, 34, 7971Ipatkin, V.V.; Kovalev, I.P.; Ignatenko, A.V.; Nikishin.,C02Me TrSbC16,CH$12 ,-78’C (>2OO:1)76%Colander. GA; Cameron,K.O. J. Org. Chem., 1993, 58, 5931M%* ,,+ (‘IAl(OC&)3 , toluene O°C,2h) o2Me Ishihm, K.; Han&i, N.; Yamamoto, H. Synlett, 1993, 127 w-h1= Z = ZMeMeMe>99% (86:14 S:R)63% Groth, U,; Huhn, T.; Richter, N. Liebigs Ann. Chem., 1993, 49 OH MeCHO , PhSH , CH-& SiO2 , rt Fuchs, K.; m.I&J. Org. Chem., 1994, 59, 528SPhSection 365Ether – Ketone347OEt C5Hdy 66%PCWP = peroxotungstophosphate Sakaguchi,S.; Watase,S.; Katayama,Y.; Sakata,Y.; Nishiyama, Y.; I&ii. Y c.I. Org. Chem., 1994, 59, 5681 N-NHCO$t7/Me1. Br2 3. 2. MeOH, NaHC03H+ 4. H30+5. DBU 77%Feuerer, A.; Sevea T, J. Org. Chem., 1994, 59, 6026 Ph k== TMSO3 eq. SnC4, -78OC,CH$l;! *PhbSPh67% m.k; Michael, J.P.; Walter, D.S. Tetrahedron Let&, 1994, 35, 5481 (~-To~)~S~, cat. Ph2CO , Yb rt ,3h. . Tanlguchl. Y,; Maruo, M.; mi.STolyl IL; Fuiiwara. Y, Tetrahedron Lett., 1994, 35, 7789KF-Al203 , t-B&OH, Pha ~v.K.;Ph0 CH2C12MeCN , 10 minPh5, PhI>K 0quantKapoor, K.K. Tetrahedron Lett., 1994, 35,948l 01. NBS, (BzO)2, CC4, heat 56% +2.1.5 Ag2C03 , MeOH , heatMe0 . Cl m. N,; Stanoeva,E.; Boeykens,M. Synthesis, 1994,427OMeCompendiumof Organic Synthetic Methods, Vo19348Section 3651. EtCH(OMe)z , TiCL4 ;~lz,-780C,lhEtzNqms2quant. 0 Hojo, M.; Nagoyoshi, M.; Fujii, A.; Yanagi, T.; Ishibashi, N.; Miura, K.; Hosomi. A, Own. Lett., 1994, 719OHW-hOAc9 CH2Cl22 snCl;!,2 NCS , -1O’C 80% (40x50synxznti) Masuyama. Y,; Kobayashi, Y.; Kurusu, Y. J. Chem. Sot. Chem. Commun., 1994, 11234fCO2Me3e4*

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. .

82%

G,; Zhang, Y.; Dreyer, G. Tetrahedron Lett., 1993, 34, 449 1 PhMezSiH , hexane, rt OSiMQPh

0 o=

(PPh3)rnH

*

Chan. T.H,; Zheng, G.2, Tetrahedron Lett., 1993, 34, 3095

(t

/ 84%

351

Ether – Alkene

Section 367

/a Pd(PEW4

0 9 W03

9 DMF

60°C , 1.5h

66%

OMe

4/

OMe

Arcadi, A.; Cacchi. S;&qock. R.C.; Marinelli, F. Tetrahedron Lett., 1993, 34, 2813 OMe w

9rt OMe I

PhCHO 0.5% Yb(fod)3

addition of K2CO3preventsformation of this Deaton, M.V.; Ciufolini. M.A, Tetrahedron Lett., 1993, 34, 2409 TM

TM 1. iBuMgBr , cat. Cp2TiC12

~TBS

70% Tani, IS.; Sato, Y.; Okamoto, S.; Sate. F, Tetrahedron Lett., 1993, 34, 4977

r(i

Me H

+

1. OSM LiC104, ether 2.1N HCl , THF 15 min, 0°C t

NHBoC

6

OTBDMS (8: 1 threo:erythro)

. PA,; Moher, E.D. Tetrahedron Lett., 1993, 34, 5567

-YOEt OEt

1. Me2S , TMSOTf , -78OC * 2. PhSLi

-yoEt

J&I. S,; Park, J.H.; Lee, J.M. Tetrahedron Lett., 1993, 34, 5769

91% SPh

Compendiumof Organic Synthetic Methods, Vo19

352

x

Section 367

OMe OMe

b

,0.3 p-TsOH

neat, rt

Bn

71%

prlohr. P, Tetrahedron Lett., 1993, 34, 6251

g

y;~p;~s

Semmelhack.ML&; Epa, W.R. Tetrahedron Lett., 1993, 34, 7205

F3

Ph aPh

SEt

+ Ph CF3

Nti,rt,2h

I.3

(94:6 Z:E)

Beg&, J.-P.; Bonnet-Delpon, D.; M’Bida, A. Tetrahedron Z&t., 1993, 34, 7753

cf

OMe OMe

OMe TMSOf , iPr2NEt -2OOC + rt ,4h

Gassman.P.G.; Bums, S.J.; Pfister, K.B. J. Org. Chem., 1993, 58, 1449 SMe

II

1. catecholborane , 3% PdClz/dppf

2* phnBr

, reflux

aq. NaOH ,2h Gridnev, I.D.; Mivaura. N.: Suzuki. A,J. Org. Chem., 1993, 58, 5351

62%

Section 367

Ether – Alkene

‘*Me3siJcc1 , BF3.()Etzw c6H 13CHO

2. DBU/LiClO&leCN , 60°C

Wl

D’AnieUo, F.; Mattii, D.; Taddei. M, Synlett, 1993, 119

Ph#‘CH$H$IH

, &CO3

PhCl , heat Billeret, D.; Blondeau, D.; Sliwa.

MeCN

~y~the~~~,1993, 881

e,

52%

==c

2. NaOMe , heat

ue.

,OMe

1. MeOH, HCl,, , ether O°C,5d

OMe

Joglekar, B.R, Synth. ~u~~~~., 1993, 23, 1979

, PhH ) 100°C

Bu

3c Bu

sealedtube 6Me

62% ’

Harvey. D.F,; Neil, D.A. Tet~uhedr~n~ 1993,49, 2145

Ji, J.; b. X, .I. Chem. SW. Chem. Comun.,

0

1993, 764

NaOCl , Mn(salen) cat. 45% (64% ee)

I ether f 4-Ph-p~dine-N~xide Chang, S.; Heid, R.M.; bobsen. E.W, Tetruhedr~~ Lett., 1994, 35,669 Ph-C&H , PhH , 90°C ph/s-+ AIBN , sealedtube Ph 2h 23% 65 Benati, L.; Capella, L.; Montevecchi, PC; Spagno~o,P. .I. Org. Chew., 1994, 59, 2818 Ph/SH

354

Compendiumof Organic Synthetic Methods, Vol9

Section 367

Lee, G.H.; Choi, E.B.; Lee. E.: Bak. C,S, Tetrahedron L&t., 1994, 35, 2195 PhSH , Pd(OAc);! THF,50°C,14h

*

72%

Backvall. J.-E,; Ericsson, A. J. Org. Chem., 1994, 59, 5850 Br

-+

Ph

C02Me

CR-

Ph Ni(C0)4, MeCN , MeOH

76% (80:20 cis:trans)

Ni(C0)4, TlOAc , MeOH 66% (30:70 cis:trans) Llebaria, A.; Camps,F.; Moreto, J.M. Tetrahedron Lett., 1994, 35, 4011

De-A,:

HO

= Iz TMSOTf , CHg12, -76OC HO :ee = OH i)H 94% 94% (>99:1 a$) Toshima. IK; Ishizuka, T.; Matsuo, G.; Nakata,M. Tetrahedron Lett., 1994, 35, 5673 SPh +

CuOTf , PhH/THF ,25OC, 0.3 h

SPh

SPh an alternative to cuBreMe$ &hen. TJ Shook, C.; Thiruvazhi, M. Tetrahedron Lett., 1994, 3.5, 6041

mez.

SPh 99% SPh

ijc, :.:g::** 0 G,; Figadere,B.; Cl&y, P. Tetrahedron Lett., 1994, 35, 6295

Section 367

355

Ether – Alkene

1.2 q. ZuEt2 , cat. Ni(acac);?, THF 2.CuCNe2LiCl

Vaupel, A.; Knochel,.

T~trah~d$~n Lett., 1994, 35, 8349

PhSLi , LiC1 , Pd(PPh3)4

*

OTf

SPh

Tl-IF , reflux 89% A.G; Barciua, LO.; Cerezo,A. de F.; Su~r~~ian, I&R. ~y~~e~~, 1994, 561 1. HZrCp2Cl , THF 25OC, lh c6b-+==

2.

cx 0

Pereira, S.; Zheng, B.; &&m&J&J.

Cl’

*

Z-02

0, 0 wl3

76%

Org. Chem.,1995, 60, 6260

CpzTiMe2, THF ,65OC OMe

OMe 67% Petasis.N.A,; Lu, S.-P. Tetrahedron Lett., 1995, 36, 2393 M!vlPP , MeOH, rt

MMPP = mouoperoxyphthalatehexahydrate TYAnnibale, A.; Scettri. A, Tetrahedron L&t., 1995, 36,4659

YmrsoJc

91%

ems *

Ph

SnClz-AcCl , CH$$ ,4h 66% yama. T,; Ishiwata, A.; Sam, T.; Matsuda,T.; Takahashi,M.; Koga, G. Tetrahedron Let& 1995, 36, 5581

Section 368

Com~n~um of Organic Synthetic Methods, Vol9

356

S

W(OAr)(OPr)(CHCMe3)Cl(OEt)2 5c

ms-

quant.

0

Leconte, M.; Pagano,S.; Mutch, A.; Lefebvre, F.; met. 132, 1069

J.M Bull. Sot. Chim. Fr., 1995,

Section 18OA(Protectionof Ketones)

RelatedMethods:

HALJDE, SULFONATE – HALIDE, SULFONATE

SECTION 368:

H~~ycloprop~a~ons are found in Section74F (Alkyds from Alkenes). Cl&XC13 , toluene ,3h mph Sakai,;

Cl,&Ph 41% RuC12(PPh)3)3 , 120°C2, Sugimoto, K.; Shigeizumi, S.; Kondo, K. Tetrahedron L&t., 1994, 35, 737 1. Cl2 , NF3*OEt2

Cl

N-OH

-0

82%

2. HCI

Cl

Tordeux, M,; Boumi~e, K.; Whelp.

0

NOH

C,J. Org. Chem., 1993, 58, 1939 F

NO’BFi , PPHF

80% F

* (>< PPHF = pyridinium polyhydrogen fluoride York, C.; Prakash,G.K.S.; Wang, Q.; Olah. G.A,Synlett, 1994, 425

0I

Br

C l&XMe3Mn04 , Me3SiBr * CH2C12,O*C

Hazra. B.(lli; Chordia, M.D.; Bahule, B.B.; Pore, VS.; Basu, S. J. them. Sot., ~erkin Trays. l., 1994, 1667 /,

KIC12, Hfi )

Ph -I

/–Cl

/+–I +

Ph

I 1) 94% _Zefirov.NS,; Sereda,G.A.; Sosonuk, S.E.; Zyk, N.V.; Likhomanova, T.I. Synthesis, 1995, 1359 Cl

(6

.

Section 369

Halide – Ketone

SECTION 369:

357

HALIDE, SULFONATE – KETONE 0

Cl hexane, rt

d

N I

92%

Cl

de Faria, A.R.; Matos, C.R.; Correia. C.R.D, Tetrahedron Let?., 1993, 34, 27 NBS , aq. MeCN , cat. HCI C02Et

rt ,6h

Br-C02Et 81%

-ton.

H.E.; Leanna, M.R. Tetrahedron Let?., 1993, 34,448l

1. ClCH21, MeLi , -78OC 2. MesSiCl , -78OC-+ rt

TMS

Et Cl

OEt * + Br Br Barluenm. J,; Pedregal,B.; Concellon, J.M. Tetrahedron Let?., 1993, 34,4563 OH Br 0

83%

HTIB ,12, MeCN , r-t; reflux ,20h F

HTIB = hydroxy p-tosyloxyiodo benzene

Bovonsombat, P.; &lcN&s. L Tetrahedron, 1993, 49, 1525 1. pyridinium polyhydrogen fluoride ‘O-c=)-’

2. :;;c,,, 3. &CO3

*

‘={rx–

61% Karam, 0.; Jacauesv.J.-C,; Jouannetaud,M.-P. Tetrahedron Let?., 1994, 35, 2541 Ph

1. PhCHO ,5% (BiC13*1.5ZnCl2) Ph y-y” zc 2. Me$iCl 0 Cl Le Roux, C.; Gaspard-Iloughmane,H.; Dubac. J, J. Org. Chem., 1994, 59, 2238

>88%

358

0 II ph/SvF

1.2 LDA ) THXWMPA ) -78°C 2. CgH1qcHU c

0 F

3. FVP (5~8OC) Reutrakul, V&; Kruahong, T.; Pohmakotr,M. Te~r~~e~~o~ Lett., 1994, 35,4853

82~48%

~~*~z,~Hz~~z rt , overnight 49% conversion Bovonsombat,P.; Angara, G.J.; McNelis. L Tetrahedron Mt., 1994, 35, 6787

NBS Yt-BuOH ) 30°C 1.5h

54%

,,

Coss~=J; Furet, N, ~~t~~~edru~ ~tt.~ 1995, 36, 3691 1. HZZrCp;1Cl 2. A&l, 15%CUB~~SM~~ w

3. NBS

Br C6h3

+

93%

zheng, B.; ~rebnik. M, Tet ra hed ran Lett., ~995~ 36, 5665

2.2 eq. FeCf3) DMF

fl;

-4m

Thompson, D.F. J, Chem,Sot., &&in Trans. -I., 1995, 23 15

f-j

Section 371

Halide – Nitrile

359

0 DMSO , (CoC1)2 t MeOH 93%

0 NEt3 , CH2C12, -6OT Raina, S.; w.

*

~

Cl

V.EL. Tetrahedron, 3995, 51, 2467 Ff12-HCO,H ,

30-lS*C ,2h * F

70% Chambers, R.D.; Greenhall, M.P.; Hutchinson, J. J. Chem. Sot. Chem. Conmun., 1995, 21

SECTION 370:

SLIDE,

SULFONATE – NITR~E

NO ADDITIONAL

SECTION 371:

EXAMPLES

HALIDE, SULFONATE – ALKENE 1. LDA 2. CIP(O)(OEt)2 0

I 3. TMS-I

Lee, K.; Wiemer. D.F, Tetrahedron Let?., 1993, 34, 2433

LDA , ether

Br Shino~u~, H.; ~

~t~oto.

K, Tetrahedron Let?,, 1993, 3#,4985

1. C13CCN 2.12 ) &CO3, ether b-

+ H

76% x 88% 7h5 C7H15

(33 Friesen. R-W,; Giroux, A.; Cook, K.L. Tetrahedron Let?., 1993, 34, i983

83%

360

Compendiumof Organic Synthetic Methods, Vol9

Section 372

85% O- F.-T,; Kumar, KA.; Hsieh, L.-C.; Wmg, R.-T. Tetrahedron Lett., 1994, 35, 2553

cat. Pd(OAc)z ‘ILiCl a+ G benz~uinone , 20°C $ t AcOH-acetone IBackvall. J.-E&;Nilsson, Y.I.M.; Andersson,P.G.; Gatti, R.G.P.; Wu, J. Tetrahedron Lett., 1994, 35, 5713 0

0

Iz,CAN,MeCN,5h reflux

I 55% (67/33 dlkwso)

6

C6h3

SiMe3

IPy2 BF4/2HBF4 , CH2C12

I

C6hJ

w

w

77% ~~~~~n~~ J,; ~v~ezaG~c~a, L.J.; Gonz~ex, J.M. Tetrahedron Lett., 1995, 36,2153

1. ICI, CH2C12, -78OC 2. NaOMe , -78OC

*

I/n/wll

43%

reversing order of ad~tion leadsto 38% of Z-iodoalkene Stewart, SK.; ~ SECTION

C3H-7

372:

CHO

Tetrahedron Lett., 1995, 36, 3929

KETONE

– KETONE

[email protected], CoCJ2

MeCN Bhatia, B.; Punniyamurthy, T.; -1.

* C3H~~c~7

+

0 15% J, J. Org. Chem., 1993, 58, 55 18

C3H7~cH3

61%

0

361

Ketone- Ketone

Section 372

2 PhLi, THF , 20°C

30 min

eswff.

2

Ph

Ph

95%

*

-R0 UT,; Zhou, M. Tetrahedron Lett., 1993, 34, 571

Ph

P+MgBr THF , -7OOC

60%

RJtL; Iyer, V.S. Tetrahedron Lett., 1993, 34, 3683

OTMS

Bn

kc

9 Fq(W9 CO, ether I 2h

0 Zhou, T.; Green. J.R, Tetrahedron Lett., 1993, 34,4497

Ph

ph~oH

, DMF , O°C Mn(pic)s /

Ph Iwasawa, N.; Hayakawa,S.; Funahashi,M.; Isobe, K.; Narasaka. K, Bull. Chem. SOC.Jpn. 1993, 66, 819

Mohr, B.; Enkelmann, V.; Wegner. G, J. Org. Chem., 1994, 59, 635

Section 373

Com~n~um of Organic Synthetic Means, Vol9

362

OTMS

J

a

OTMS

*

0

BFs*OEtz

61%

J, Org. Chem, 1994, 59, 1485

Jenkins, T.J.; Burnell.,

0

0

Yb-TMS-Br 68%

THF , reflux I

K

Tanigychi. Y,; Nakahashi,M.; Kuno, T.; Tsuno, M.; Makioka, Y.; Takaki. K.: Fuiiwara. Y, Tetrahedron Lett., 1994, 35,411l OAc

Maikap, G.C.; Reddy, M.M.; Mu~opadhyay, M.; Bhatia, B.; &b&& 9145

Tetrahedron, 1994, 50,

H PCWP, DCE , reflux ,3h Bu

Bu + OH

mp

= bC5fkN(CH2)15Md3

Iwahama, T.; Sakaguchi,S.; Nishiy~a, Y.; m.

93% (~4~(0)(02)2bl 0 Y, T~tr~hedr~~ Lett., 1995, 36, 1523

REVIEW:

“a-Diones from Cyclic Oxamidesand ~g~o~i~iurn Reagents:A New, Generaland Environmentahy Beneficial Synthetic Method,” ~r=West~. UT,; Zhou, M. ~y~Ze~, 1994,975

SECTION 373:

KETONE

– NITRILE

, DCE ,70aC t 20% Pd(OAc)2nPPh3-dppb 65h LL Org. ~he~.~ 1994, 5%2679 Nozaki, IS.; Sato, N.; ma.

Ph

Phe

0

74%

Section 374

SECTION

Ketone- Alkene

374:

KETONE

363

– ALKENE

For the oxidation of allylic alcohols to alkeneketones,seeSection 168 (Ketones from Alcohols and Phenols) For the oxidation of allylic methylenegroups (C=C-CH2 + C=C-C=O), see Section 170 (Ketonesfrom Alkyls andMe~ylenes). For the ~yla~on of alkeneketones,also seeSection 177 (Ketonesfrom Ketones)and for conjugatea~ylations seeSection74E (Alkyls form Alkenes).

4 Meo2cer-o

PdC12(PhCN)2) 50°C SnC12,MeCN y33h Masuvam~ Y,; Sakai,T.; Kurusu, Y. Te~r~~e~~~~ L.&t., 1993, 34,653 OCO2Me

Das, N.B.; Sarma,J.C.; Sharma. R.P,; Bordoloi, M. Tetrahedron Lett., 1993, 34, 869

w

SnBu3

)

AIBN

m.

G.A.; Andersh, B.; Su, Q.; Shi, J. Tetrahedron Lett., 1993, 34, 1741 P 1.

wm5 ?== Me0 50°C ,3h, SiO2

2. CAN, O.lM aq. HNO3 rt, 20 tin Harrity, J.P.A.; Kerr, W.J,; Middlemiss, I>. Tetrahedron Lett., 1993, 34, 2995

86%

364

Com~n~um

&

C02Et

of Organic Synthetic Methods, Vol9

Section 374

1. PhH , Cu(OAc)[email protected]@ Pb(OAc), ,2d

CO2Et

2. ethylene glycol , CH2C12

* & Schultz, A.G.; Holoboski, M.A. Tetrahedron Lett., 1993, 34, 3021

MI-O, CHfl12, rt t

-+*,,,w

SiOdA1203

MT0 = methyltrioxorhenium Junga, H.; Blechert. S. Tetrahedron Lett., 1993, 34, 3731

Mo(C0)6 , DMSO , Toluene 100°C ,12h Jeonrr. NJ Lee, S.J.; Lee, B.Y.; ~hung, Y.K. Tetrahedron Lett., 1993, 34,4027

Br

Yu, Y.; Lin, R.; m.

SmIy,THF,rt,2h 02N*cHo

*

p~No2

Y, Tetrahedron Lett., 3993, 34, 4547

CHCl3 , rt ,8h

TBDMSA

TBDMS

Konopelski. J.P,; Kasar, R.A. Tetrahedron Lett., 1993, 34, 4587

78OC

Section 374

Ketone – Alkene

365

BufinH , AIBN, 60°C syringe pump (3h) ,O.O2M

Rawal. VH,; Zhong, H.M. Tetrahedron Lett., 1993, 34, 5197

Bu3s-YoEt I Bu 3SwOEt

hJL hJL

n

OEt

OEt P 0.01 PdCl2(MeCN)2, 20°C 75% * * DMF ,2h OEt Par-rain, J.-L.; Beaudet, I.; Duchene, A.; Watrelot, S.; Quintard, J.-P. Tetrahedron Lett., 1993, 34, 5445 P

Cl

FLke2

CF$E 88%

CH2C12, reflux ,96h Ales, C.; Janousek, 2.; Viehe. H.G. Tetrahedron Lett., 1993, 34, 5711

CF?

1. BuMgBr , 10% CuI, TMSCl HMPA , THF , -78OC 2. CH212 ,2 eq. Et2Zn

biker-Milbum.

))

c

3.2.2 eq. FeC13 , DMF , O°C – B+3=099x93x54% 4. NaOAc , MeOH M.1,;Thompson, D.F. Tetrahedron Lett., 1993, 34, 7291

slzN&$ fast addition

(2:l z:E) 70% Sha. C.-K,; Shen, C.-Y.; Jean, T.-S.; Chiu, R.-T.; Tseng, W.-H. Tetrahedron L&t., 1993, 34, 7641

366

m;

Com~n~um of ~g~ic

Syn~e~c Means, Vol9

Section 374

Kassir, J.M.; Semones,M.A.; Weing~en~ M.D. T~~~~~~~r~~L&t., 1993, 347853

; Riesinger, S.W, J, Org. Cafe,, 1993, 58, 408

Me

11

.*

27)

~7%

Ihle, NC.; Heathcock. CH, J, Org. Gwen., 1993, 58, 560

( Ew~2zn EtQgz

II

Bu CuBrGMe2, HMPA TMSCl

C02Et 65%

C~mmins. M.T,; ~~te~et, P,XX; Trotter, B.W.; Vatlin, I.M.; Watson,P.S.; McKerlie, L.A. Reinhold, T.L.; Cheung, A.W.; Stetson,K.A.; Dedcpoulou, D.; Gray, J,L. J, Org. Chem., 1993, 58, 1038

Section 374

Ketone – Alkene

367

0

0

53%

2.2 eq, CuSO4, llO°C Trost. B.M; Parquette, J.R. J. Org. Clef.,

1993, 58, 1579

co2(c0)8, MeCN rt -9 75OC

91% *

Me

0

Hove. T.R,; Suriano, J.A. J. Org. Chem., 1993, 58, 1659

2 eq. PhCHO , ZrOC&8 IT20

Ph 73%

Yuki, T.; Hashimoto, M.; Nishiyama, Y.; Ishii. Y,J. Org. Chem., 1993, 58, 4497

Ph

z=z=

Ph Ph

5% Pd(OAc)z ,4 NaOAc 100°C, DMF , BQNCI 84%

Ph

Larock, R,C; Doty, M.J.; Cacchi, S. J. Org. Chem., 1993, 58, 4579 0

Bu

W(CO)6, THF , CO, sealed tube BU

hv ,65OC j,

llO°C

J. Am. Chem. SW., 1993, 115, 1154

0

Co~~n~u~

368

TMS

of Organic Syn~e~c Mean,

PhC=CH , S&14-NBu3

w

~ l .

-A.;

I

Section 374

Vo19

Ph

~ 85% (203 Ez)

’ Hirarna, M. J. Am. Chem. Sot., 1993, 115, 3362

0 In–f

0 Ph

5% RhCl(PPh3)3,toluene , 120°C

Ph *

3 huffs,

~ 84%

M.A.; ~,ie~eskind. L.S, J. Am, ~~~~* Sm., 1993, 115, 4895 Me$KN Cp2Ti(PMe&

Berk, S.C.; Grossman,R.B.; Buchwald. S.L,J. Am. Chenz. Sm., 1993, 115, 4912 COzMe

CO, 10% Pd(OAc)z-dppp Phi-MeC~-MeOH

r

&&U&N. T,; Tsuji, J.; Tsujiguchi, Y.; S;zito. S, J. Am. Chem, Sm., 1993,

TiC14, CHg12, -40°C, lh

81% 0 115,

5865

C02Et

OMe funk. I?J& Fingered, J.F.; Olmst~ad,T.A,; Para, KS,; Wos, LA. J. Am. Clef. Sot,, 1993, 115,8849

Ketone- AIkene

Section 374

I B”

II

~

369

, 10% (c~)CpRuCI OH

20% NH4PF6, neat, 1OOOC

Bu

B-M,; Martinez, J.A.; Kulawiec, R.J.; Indolese, A.F. J. Am. Clef. Sot., 1993, 115, 0

PhCHO ) SnCIz , Na2SO3

Br Ph~ Lin, R.; Yu, Y.; Zhang Y, Wyatt, C~~~~.,

PhTPh

73%

0

1993, 23, 271

tduene , sealedtube ,23”C -+ 50°C

Srikrishna. A,; Krishnan, K.; Van Kateswarlu, S. J. Chem.Sm. Chem. Coals.,

&

1, D;ue

1993, 143

, SnQ- Bu3N

70%

~~

Ph auchi. MJ Sehata,M.; Hayashi, A.; Hirama, M. J. Chem.Sot. Chem. Comnzun.,1993,

Bu’–(

PPh3, EtOH , PhH 0

reflux

72%

0

Guo, C.; Lu. X, J. ~~~. Sm., Pe~~~~Trans. I., 1993, 1921 +gb+%-

SePh

SnBug

AIBN , toluene

Watanabe,Y.; Yoneda, T,; Okumura, T.; Ueno, Y.; Tom T, Butt. Chem.Sm. Jpn., 1993, 66, 3030

370

Compendiumof Organic Synthetic Methods, Vo19

Section 374

H

0

0.01 mol dmB3 toluene , reflux

b&&&u&;

a I-f

-~

0 53% Takada,K.; Odagaki, Y,; hoe. S, .I. Chem. Sot. Chem. Commun., 1993, 556

l

0 2. 3. 1. BuGnOSnBu3 PhCHO H20 , (-C02) , HMPA 0 Nishio, M.; Baba, A.; Mats&a, H. Chem. Lett., 1993, 1219

%0 mT.:

62%

t

1. Me&I , CHQ , rt ,30 min 2. PdC&(MeCN)2,9h

4

SiPh3

siPh3

w

/

64%

Degl’Innocenti, A.; Capperucci,A.; Bartoletti, L.; Mordini, A.; Reginato,G. Tetrahedron Lett., 1994, 35, 2081

CM% 6

~seo2H~p~~~

~OH

+ ~

leq.,rt,14h 35% 2 eq., 20°C, 14h 20% 2 eq. , reflux ,2h Barton. D.H.R; Wang, T.-L. Tetrahedron Lett., 1994, 35, 5149

36% 75%

90%

Li

0

Ph~

e(

me2

OEt

*

Ph j;r

enolate free a-alkoxy vinyllithium reagent improved prep & procedure Shimano, M.; Meye;rs.AJ, Tetrahedron Lett., I994, 35, 7727

OEt 90%

Section 374

Ketone- Alkene

371

I

C5Hll

TMSCl , MeCN , rt ,3h Me -c

I o. F.-T,; Hsieh, L.-C. Tetrahedron Lett., 1994, 35, 9585

3% co2(co)fj

co,

EtOg

w

3, DME , Id

92%

0

Eto

EtO?C 82%

Jeong. N,; Hwang, S.H.; Lee, Y.; Chung, Y.K. J. Am. Chem. Sot., 1994, 116, 3159 Ph CpzTi(PMe& , Schlenk tube Me$iCN , PhH 80%

Berk. S.C,; Grossman,R.B.; Buchwald. SL, J. Am. Chem. Sot., 1994, 116, 8593 NHMe Meu

1. PhMgCl , CeC13, -78OC, THF * 2.10% AcOH

Me

MYYMe Ph

0 85%

Bartoli. Cr,;Cimarelli, C.; Marcantoni, E.; Palmieri, G.; Petrini. M, J. Chem. Sot. Chem. Commun., 1994,715 I!!7

0

0

3. 1.MeCH(Cl)SPh KH CO2Me

2.ZnCl2

4. DABCO

c!b Amecke, R.; Groth. I J,; Kohler, T. Liebigs Ann. Chem., 1994, 891 MST J= C3H7

*

90×88%

TiCI4 , LiAlH4, CC4 CHEt

C3H +

f4=i

Mitani. M,; Kabayashi, Y. Bull. Chem. Sot. Jpn., 1994, 67, 284

63% (2)

Cl

Et

Section 374

Compendiumof Organic Synthetic Methods, Vol9

372

16 /l/I

,rt,3min [email protected]

2.MeOH,rt,3min 3.0.1 N aq. HCl , rt 3 min

.

(9

1) 84%

Miyoshi, N.; Takeuchi. S,; Ohgo, Y. Bull. Chem. Sot. Jpn., 1994, 67, 445 PhCHO , Ni(cod)zPPh3, Zn

*

ph-Y 52% OAc 0 Masuyama. Y ,; Sakai, T.; Kato, T.; Kurusu, Y. Bull. Chem. Sot. Jpn., 1994, 67, 2265 dioxane ,6O*C, 4d

0

2 eq. Mn(OAc)s , Cu(OA& * AcOH ,8O*C

c

CD 0

52%

er. B&; Cole, B.M. J. Org. Chem., 1995, 60, 5376

C -I.;

t-BuMe$iH , Rh4CO) 12 CO, PhH , reflux 14%

63% Ishibashi, H.; Ii, N. Tetrahedron Lett., 1995, 36, 241 0

0 A

x

co(co)4

NaH **

X=NHTs X can also be OH, CHNO2, C(CO2Me)z Bates. R.W,; Devi, T.R. Tetrahedron Lett., 1995, 36, 509

X=NTs,69%

Section 374

Ketone- AIkene

373

2.25 CAN, DMF , O°C, 1.75h

F-vans.P.&, Longmire, KM.; Modi, D.P. Tetrahedron Lett., 1995, 36, 3985 0 e’ , clots 81% –

SiMe3 Chueh, L.L.; Tsay, S.-C.; fIwe

Lin.; .,,c7c15

C02Et

4

SiMe3

Tetrahedron Lett., 1995, 36,4093

PPh3m-hul~

,“,“,”

I toluene

ylyco2Et #

82% SaW, M.K.E.; j?elIicciari. R, Tetrahedron Lett., 1995, 36, 4497

Resek,J.E.; Mevers. A& Tetrahedron Lett., 1995, 36, 7051 OMOM EtO$-

ZnI

Me$iCl , CuCN , HMPA EtO$~;

l

.

68%

Huang, S.; Guise, L.E.; Lacy, D.B. Tetrahedron Lat., 1995, 36, 7061 0

Ph-Bt Bt = benzotriazole

1. BuLi * 2. cyclohexanone, ZnBr2, toluene llO°C, 12h c

60% Katritzkv. A.R,; Xie, L.; Toader, D.; Serdyuk, L, .I. Am. Chem. Sot., 1995, 117, 12015

Ph

374

Compendiumof Organic Synthetic Methods, Vo19

iPrNO2, DBU , MeCN

Section 375

4

65%

rt ,4h

Balllnl.,

Bosica, G. Tetrahedron, 1995, 51,4213

78%

Bates, R.W,; Rama-Devi, T.; Ko, H.-H. Tetrahedron, 1995, 51, 12939

8% MeReO3, C13CCF3

reflux ,5d 80%

Schneider,M.F.; Junga, H.; Blechert. S, Tetrahedron, 1995, 51, 13003 Ph Ph

=

Ph

, toluene ,135OC

WH)2(CW’P~3)3 7lh

85% (9:l)

Kakiuchi, F.; Yamamoto, Y.; Chatani, N.; Murai. S, Chem. Lett., 1995, 681

SECTION 375:

NITRILE – NITRILE NO ADDITIONAL EXAMPLES

375

Nitrile – Alkene

Section 376

NITRILE

SECTION 376:

– ALKENE

l.LDA,THF, 3 eq. HMPA , -78OC

phTCN

2. Me1 , -78OC

NMePh

*

,mcN

81%

NMePh

Me 100% z

Chang, C-J.; Farm, J.-M,; Liao, L.-F. J. Org. Chem., 1993, 58, 1754 I. PPh3, PhH ,rt PhhN3 I Ph

2. Ph$=C=O , PhH , rt

51% Molina. P,; Alajarb, M.; Lbpez-Leonardo, C.; AlcGntara, J. Tetrahedron, 1993, 49, 5153 1. Me$iCH2MgCl,

THF , -2OOC 36%

2. PC13, THF ,67OC so. H.-E, Gilbert, B.A.; Hwu, JR. J, Check Sot. Clef.

C~~~n.~

1993,669

2 LiCN ,0.07 Pd(PPh3)4 0.07 12-crown-4

UTf

CN

PhH,rt Piers. E,; Fleming, F.F. Can. J. Chem., 1993, 71, 1867 CN Cl

/==-c

CN

0

CN

c.3

MezN=CClz Cl, CH$& 2 eq. NEt3 , -15*c

Cl *

Me2N

+

79% Bouvy, D.; Janousek, 2.; Viehe, H.G. ~~~2,Sot. Chum. Belg., 1993, 102, 129

Yamamoto. Y;, Al-Masum, M.; Asao, N. J. Am. Chem. SM., 1994, 116, 6019

CN

Section 377

Cum~n~um of Organic Synthetic Methods, VoI 9

376

1. Pd&dba)3eCHC13 , 10h

Me

a 2. /y/Pr

,4%CuI,2eq.~,D~

PdCI(PPh3)~CH~h), rrt ,4h Suginome,M.; Kinugasa, H.; Ito. Y, ~e~r~~e~r~~Lett., 1994, 3.5, 8635

Et02C/CN

-CHO

, TfQT

* *co2Et 6% RuH2(PPh3)4 83% b ur&&hi. . S. I.: Naota, T.; Taki, H.; Mizuno, M.; Takaya, H.; Komiya. S,; Mizuho, Ye; Oyasato, N.; Hiraoka, M.; Hirano, M.; Fukuoka, A. J. Am. Chem. Sot., 1995, 117, 12436 Ph-

KCN , DIvIF , NiBr2(PPh3)2 * Zn , PPh3, 50°C

Br

PhwcN

99% (95f5 En) Sakakibara,Y.; Enami, H.; Ogawa, H.; Fujimoto, S.; Kato, H.; Kunitake, K.; &saki. K,; Sal& M. Bull. Chem. Sot. Jpn., 1995, 68, 3 137

SECTION 377:

ALKENE

– ALKENE

1. (Me2N)+CHZ 4 eq. NaN(SiMe3)2

*

C13TiO 2. 5

eq.

c3

CHO

Reynolds, K.A.; Dopico, P.G.; Sunde~ann, ML; Hughes, K.A.; Finn. M,G,J. Org. Chem., 1993, 58, 1298 1. Cp2ClZra GoH21–CHO

SnBug

CH2C12 2. BF3*OEt2 Maeta, H.; Hasegawa,T.; &uki. M, Synlett, 1993, 341

D-

c a21

N

92% (96:4 EZ)

Alkene – Alkene

Section 377

377

Bu

OTIPS

Bu (cod)RuCpCl

mt.

..

11 R .W; Indolese, A. J. Am. Chem. Sot., 1993, I 1.5, 4361

4) 68%

Ph ,OPh (fp

0 -20°C , lh

C7Hl 4 Yanagisawa, A.; Hibino, H.; Nomura, N.; Yamamoto. H, J. Am. Chem. Sot., 1993, IIS, 5879

ZnCl PdW’bh , m–n?,rt Mazal, C.; Ultier.

M, Tetrahedron Lett., 1994, 35, 3089

B” Bu

=

Bu 3. cat. CuCV2LiCl , hcl 50°C, lh

Bulc 87%

Takahashi. T,; Kotora, M.; Kasai, K.; Suzuki, N. Tetrahedron Lett., 1994, 35, 5685 Br 1. CjH llMgB , NiClz(dppe) , THF 2. PhMgBr , NiQ(dppe)

Ph

PhS/ W-h */ 52% Babudri, F.; Fiandanese,V.; Mazzone, L.; Naso, F, Tetrahedron Lett., 1994, 35, 8847

378

Compendiumof Organic Synthetic Methods, Vol9

Br

$”

Section 377

Ph

, Pd(OAc)2, 10 kbar ,2d

PPh3, NEt3, TI-WMeCN , 20°C * c Voigt, K.; Schick, U.; Meyer, F.E.; de Meijere, A. Synlett, 1994, 189

0

Schmitz, C.; Harvey, J.N.; Viehe. H.G. Bull. Sot. Chim. Belg., 1994, 103, 105

(65 35) 91% Araki, S.; Imai, A.; Shimizu, K.; Yamada,M.; Mori, A.; Buts&an. Y,J. Org. Chem., 1995, 60, 1841

n

I

Pd(OAc)2, TPPTS aq. MeCN , iPr2NH 5

CO2Me P BU-

BuT 80%

C02Me

3

&O

Genet,J.P.; Linquist, A.; Blart, E.; Mouries, V.; Savignac,M.; Vaultier, M. Tetrahedron Lett., 1995, 36, 1443 COzEt lbleF$%~C6H13

Pd(OAc)2, PPh3,DMF ,28h rt , sealedtube Ph Matsuhashi, H.; Hatanaka,Y.; Kuroboshi, M.; Hivama. T, Tetrahedron Lett., 1995, 36, 1539

Section 377

Alkene – Alkene

379

Ph Yoshida, A.; Matsumoto, S.; Feng, IF.;Matsumoto, Y.; Sugino, A.; Hanamoto,T.;

. Mlkaml,; &

Tetrahedron

1995, 36,907

ktt.,

/

OSiMe3 d-

SiMe3 w

10%ZnClz , CH$& 25OC, L5h Ph

+ f I Ph

(22

.

78) 94%

Furuhashi, K.; Natsume,H. Tetrahedron L&t., ;995, 36, 5243

BT.;

I

Bu

Bu OH

, IXvlF:Hz(,

C3H+V

5% Cp~u(~)Cl

, loo°C

C3H7

st. B.M; Indolese, A.F.; Miiller, T.J.J.; Trepton, B. J. Am. Chem. Sot., 1995, 117, 615

Bu

ZZZ

Bu

1. Cp2ZrEt2 2. CHz=CHOEt

Bu

Bu w

3. H+

m

.

50%

T; Kondakov, D.Y.; Xi, 2.; Suzuki, N. J. Am. Chem. Sue., 1995, I1 7, 5871

380

Compendiumof Organic Synthetic Methods, Vo19

Me$i

=

WoPh

Section 377

9 PMe3

w-h3 CPa-BU2

81% Suzuki, N.; Kondakov, D.Y.; Kageyama,M.; Kotora, M.; Ham, R.; Takahashi.T, Tetrahedron, 1995, 51, 4519 Ph 10% RhCl(PPh3)3,PhMe

*

110°C * 80% Wender. P.k; Takahashi, H.; Witulski, B. J. Am. Chem. Sot., 1995, 117, 4720 1. TaCl5 , Zn , DME , PhH 2. THF w-h-w11

3. -0

Li+

4. aq. NaOH 65% T.&G. K,; Yamada,M.; O&&a, H.; IJtimoto. K,; Fujii, T.; Furukawa. I, Chem. k-K 315

19%

1. :cc12 C6H1-TMs 2. CsF 9DMF * cald/ . . m. &; Kobayashi, Y.; Koyama, K. J. Chem. Sot., Perkin Trans. l., 1995, 653

(95

.

72%

5) 86%

Yanagisawa,A.; Hibino, 1-I.;Habaue,S.; Hisada,Y .; Yasue, K.; Yamamoto.H, Bull. Chem. Sot. Jpn., 1995, 68, 1263

381

Oxides – Alcohols

Section 380

OXIDES – ALKYNES

SECTION 378:

0 * piTo Leonine,

1.2eq. Bu$nC=CBu , DMF 2% Pd(MeCN&12 rt,30min

l

SECTION 379:

77%

J.A.; Ventura, M.P. Te~ra~edrun Let& 1993, 34, 3663

OXIDES – ACID DERIVATIVES NO ADDITIONAL EXAMPLES

SECTION 380:

OXIDES – ALCOHOLS, THIOLS

Domfnguez, E.; w.

J.C Tetrahedron Lett., 1993, 34, 5803

OEt / P– OEt

MePO(OEt)z, BuLi , THF BF3*OEt2,-78OC

0

Li, 2.; Racha, S.; Dan, L.; El-Subbagh, H.; Abushanab.

MeO-PhCHO

83%

J. Org. Chem.,1993, 58, 5779

R

P Me0

H

+ 10%Li binaphthalenide, TI-IF

Ph

Me&’ Me0v

98% (20% ee) OH

Rath, N.P.; Spillincr. C.D, Tetrahedron Lett., 1994, 35, 227 0

, SmI2,THF

S02Ph 71% Te~ra~edrun Lett., 1994, 35, 5441

382

Compendiumof Organic Synthetic Methods, Vol9

Section 380

OH = E P

3.3 eq. La-Li-(R)-BJNOL complex MeNO*, THF , -40°C, 72h

CHO NPhTh

-+

NPhTh

NO2

99%

(99:l erythro:threo; 96% ee) N Tetrahedron Lett., 1994, 35, 6123

Sasai,H.; Kim, W.-S.; Suzuki, T.; wi.

l.LHMDS,O”C 2. PhCHO , 0°C 3. HCl , EtOH

92) 62% (8 VJ$.; Worrall, J.M.; Adams,H.; Alexander, R. Tekahedron Lett., 1994, 35, 6167

-al.

0

1. EtLi

0

0 t

P Ph’ II1Jk Ph

3.10% AcOH 2. CeC13, THF , -78OC

OH

P Ph’ II14 Ph

Et

71% Bartoli. G,; Sambri, L.; Marcantoni, E.; Petrini, M. Tetrahedron Lett., 1994, 35, 8453 vyOH

H202

OH . . ovicelll.

; w.

.

9 TS-1

4oH * 0

TS-1 = metal dopedzeolite

quant. P,; Sanetti, A.; Mincione, E. Tetrahedron Lett., 1994, 35, 8477 Ph S02Ph 1.2BuLi,THF

# Ph

2. t-B&OH, 15h -7OOC+ 2o”c 90% (55:45 erythro:threo)

Chemla, F.; Julia. M; Uguen, D. Bull. Sot. Chim. Fr., 1994, 131, 639

Section 383

Oxides – Amines

383

Bakers yeastI 4h

tiNo2

74% (99% ee , S)

uama. A,; Occhiato, E.G.; Spinetti, L.M.; Vallecchi, M.E.; Scaarpi, D. Tetrahedron, 1995, 51, 1775

SECTION 381:

OXIDES – ALDEHYDES CO/H2 (600 psi) , CH2C12 98%

Totland,K.; A,lpgr. )t J. Org. Chem., 1993, 58, 3326

SECTION 382:

OXIDES – AMIDES M BnNH2, NaH ,2.5h

9R 99

) TolO$ NHBn Me%,,, TolO$ + 82% * Cl Satoh, T.; Motohashi, S.; Kimura, S.; Tokutake, N.; Yamakawa, K, Tetrahedron Lett., 1993, 34,4823 1. CAN, MeCN , NaN02, Id 2. Hz0

NO2

64% NHAc Reddy, M.V.R.; Mehrotra, B.; Vankar. Y,D, Tetrahedron Lett., 1995, 36,486l

SECTION 383:

OXIDES – AMINES

,CO,Me Nw

p-TolS02SePh AIBN , PhH reflux

Brumwell, J.E.; Simpkins. N.S.; Terrett, N.K. Tetrahedron L&t., 1993, 34, 1215

Section 384

Compendiumof Organic Synthetic Methods, Vol9

P

C3HW

OEt

95°C) neat, 6Oh

Ruder. S.M; Norwood, B.K. ~e~r~~e~r~~ Lett.,

1994, 35, 3473

X

X NO2

I

bakers yeast, 4d

m

/

kv

NO2

NH2

+

I

/I

Q NO2

No,

3) 37% X = Et (1 1) 36% X = OMe (5 Davey, CL.; Powell, L.W.; Turner. NJ,; Wells, A. Tetr~h~d~o~ L-e& ~99~, 35, 7867 l

. l

N-Tr

NHTr = =

[La, BINOL , Li] , THF =c dp

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