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
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Sinaar>ore
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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
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-
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
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*
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
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$iH , Tic13 PhAA b Ph &CO,H ma–I Yato, M.; Homma, K.; Jshida. A, Heterocycles, 1995, 41, 17
NaCNBH3, THF BFyOEt;!, rt ,30 min 4
g5%
+
Me0 shna. A,; Viswajanani,
SECTION
.. 2) 85% (3 R.; Sattigeri, J.A.; Yelamaggad, C.V. Tetrahedron
163: HYDRIDES
FROM
SmI2, THF-HMPA
1995,
36,
NITRILES
This section lists examples of the reaction, R-C=N + isonitriles (R-N&). CN
tiff.,
R-H (includes reactions of
Ph
, 0°C
CN 97%
CN Ph 3 Hong, W.S.; Cho. Y.S,; Koh, H.Y. Tetrahedron Lett., 1995,
SECTION
164: HYDRIDES
FROM
ALKENES
NO ADDITIONAL
SECTION
165: HYDRIDES
FROM
H 36, 7661
EXAMPLES
MISCELLANEOUS
COMPOUNDS
Mg , EtOH , cat. HgCl2 P
rt
Lee, G.H.; Choi, E.B.; Lee, E.: Pak. C& Tetrahedron
98% Lett., 1993, 34, 4541
Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright 2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)
Section 166
Ketones from Alkynes
CHAPTER
183
12
PREPARATION
OF KETONES
SECTION 166: KETONES FROM ALKYNES
Cha. JS,; Min, S.J.; Kim, J.M.; Kwon, 0.0. Tetrahedron Lett., 1993, 34, 5113
. Tekeuchl.,
78% Yasue, H. J. Org. Chem., 1993, 58, 5386
MeCN , 760°C, 4h OMe CO)sCr
+ Me
(11:l ,33%) Kim, O.K.; 1;vulff. W.D%; Jiang, W.; Ball, R.G. J. Org. Chem., 1993, 58, 5572 0
Ph 1.10% c02(c0)8,
DME
2.20% P(OPh)3 , reflux
Iwasawa, N.; Matsuo, T. Chem. Lett., 1993, 997
0
Compendiumof Organic Synthetic Methods, Vol. 9
Section 167
1. BrzBH*SMez 2. propylene glycol Br
X
Bu
* 3. CH2=CHCH2MgCl, THF , -78OC 4. HMPT , THF , 50°C, HMPA 5. oxidation Brown. H.r; Soundararajan,R. Tetrahedron Lett., 1994, 35,6963
Bu* 95%
MeReO3, H202, tOH Ph
=
Ph
*
Ph
Ph 4f 0
80%
Zhu, 2.; EsPenson.J.ltI, J. Org. Chem., 1995, 60, 7728
SECTION 167: KETONES FROM ACID DERIVATIVES
P
Ph
pAc1 TiCl&Zn ,3% HCl
–
p)$+;
+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
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*&,’
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
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+ *
;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$X&
CN AcOH , Ac20, 10°C , Ih a&. J.-F,; Jung, L.; Hug, R. Heterocycles, 1994, 38, 297
cat. ZnC12, CH2C12,50°C16d ~y~e~ic
Pummerer rearrangement
; Shibata,N.; Kawano, N.; Tohjo, T.; Fujimori, C.; Matsumoto, K. Tetrahedron Lett., 1995, 36, 115
Section 346
Compendiumof Organic Synthetic Methods, Vo19
292
Amlres, C.J.; Spetseris,N.; Norton
SECTION 346: AMIDE – HALIDE, SULFONATE
Cl * l-L?Cl
Cl
CuCl , cat. bipy
98%
0
N
I Bn
Nagashima,H.; Ozaki, N.; Ishii, M.; Seki, K.; Washiyama,M.; Itoh, K. J. Org. Chem., 1993, 58,464
Et3N*3 HF , MeCN
77%
t e”
Narizulca, S.; Fuchierami. T, J. Org. Chem., 1993, 58, 4200
IP
Ph#e(OH)OAc , I2 hv ,6Sh ?
0
I
I
76% Dorta, R.L.; Francisco, C.G.; Suarez. IE,~etr~he~~~~ Lett., 1994, 35, 1083
a
NPh2
w ~
.
h/L; m
1. b-AnP(S)S]z, PhMe , lOO*C 2. Bum2F3, NIS , CH2C12 o”c -+ l-t T, ~etr~he~~u~ Lett., 1994, 35, 3983
F w w
x
F
NPh2 98×64%
Section 347
Amide – Ketone
293
C3H7
0 b Nt
0
-7VC, 6h BC120Me
ind Jt-
1) 80% o. G,; Di Martino, E.; Gentilucci, L.; Tomasini. C,; Tomioni, L. Tetrahedron Asymmetry, 1995, 6, 1957 (>99
l
SECTION 347: AMIDE – KETONE
0
2DMP,4Py,lh CH2Clz, rt
N
Dess-Martin
ti
)
0 N
0
periodinane
Ph
75%
Ph
,hyr DMP = 1,1,l-triacetoxy-l,l’-dihydro-l,2-benzodoxol-3(1H)-one Batchelor, M.J.; Gillespie, R.J.; Golw. J.M.C,; Hedgecock,C.J.R.
Tetrahedron Lett., 1993, 34, 167
30% H202, Pd(OAc);! CH2C12,rt ,2h –
73% *
Naota, T.; Sasao,S.; Tanaka,K.; Yamamoto,H.; Murahashl.. 4843
0
0
ii Tetrahedron Lett., 1993, 34,
OEt
w
c
0 TFA , 20°C, Id N
NT -* 0 Br 0 J.-P*;Jacquesy,J.-C.; R~nbaud, D. Tetrahedrons 1993, 49, 2239
47%
Section 347
Compendium of Organic Synthetic Methods, Vol9
294
Bu$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
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
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
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
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$& C02Et
48h, 30°C 2. aq. HCI, CHCI3 , Him-da, Y.; unhip,;
Tanaka, Y,; Ueda, I. J. Org. ~~~.,
1994, 59, 111
1. (Coa)2 , hv t
60%
2. MeOI-I
02Me ; Hardee, J.R.; Gelber, N.; Qi, L.; Axenmd, T. J. Org. Cbem., 1994, 59, 2131
ICI-I ) THF ,18-c-6 , rt
Me
4
60%
0
AC
Ph JL
OAc ,4% Pd(P~h3)2C12
Cl
w C7Hl K
SnBu3
Ph C7Hl
8% CuCN ,75”C, 18h
~
J, Am. Cam. Sot., 1994, 116, 1
Ye, J.; Bhatt, R.K.;
N c1
Ph -If
0
CO&B u
0
0
IsJr&o. B, Te&hedron
96%
L&t., 1994, 35, 5073
74%
0
332
Section 360
Compendium of Organic Synthetic Methods, Vol9
Me
Me
Mn(OAc), , AcOH 8O”C, 8h w
Me02C
0
C02Me 57%
C.-P,; Wang, S.-F. Tetrahedron Lett., 1994, 35, 4365 1, NaH , DME ,40°C 2. BuLi 3. PCC , Al203 , CHg12 93x68x68% Piers. E,; Cook, K.L.; Rogers, C. Tetrahedron Lett., 1994, 35, 8573 0 KMn04, CuSO&
Hz0 47%
4h * Das, J.; w
0
c
0
S, Tetrahedron, 1994, 50, 11709 e- , CH2C12- Hz0 NaBBr2
C02Me
C02Me 87%
Maekawa, H.; Ishino, Y.; mguchi. OH PhI-
L Chem. L&t., 1994, 1017
aq. t-B&OH, C02Et
1% CuC12,3% TBAB
CH2C12, 25OC, Id
*
PhA
C02Et 96%
Feldberg, L.; Sasson. Y, J. Chem. Sot. Chem. Commun., 1994, 1807
Section 360
Ester=Ketone
333
68% Ryu, 1; Nagahara,I(.; Yamazdci, H.; Tsunoi, S.; Sonoda. N, Synlett, 1994, 643
Bu$nH, AIBN
(9
m,
Kinter, KS. J. Org. Chem.,1995, 60, 4850 OCQMe
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
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
Section 362
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*
. .
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