Compendium of Organic Synthetic Methods -Volume 12

584 Pages·2009·19.38 MB·English

by  Michael B. Smith

Compendium of Organic
Synthetic Methods
Volume 12
MICHAEL B. SMITH
Department of Chemistry
The University of Connecticut
Storrs, Connecticut
@3
WILEY
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Library of Congress Cataloging Card Number: 71-162800
ISBN 978-0-471-44530-2
Printed in the United States of America.
1 0 9 8 7 6 5 4 3 2 1
CONTENTS
vii
Preface
ix
Abbreviations
...
Index, Monofunctional Compounds Xlll
xiv
Index, Difunctional Compounds
Introduction XV
1
1 Preparation of Alkynes
9
2 Preparation of Acid Derivatives
17
3 Preparation of Alcohols
51
4 Preparation of Aldehydes
5 Preparation of Alkyls, Methylenes, and Aryls 67
151
6 Preparation of Amides
177
7 Preparation of Amines
209
8 Preparation of Esters
9 Preparation of Ethers, Epoxides, and Thioethers 227
10 Preparation of Halides and Sulfonates 245
11 Preparation of Hydrides 253
259
12 Preparation of Ketones
283
13 Preparation of Nitriles
14 Preparation of Alkenes 289
15 Preparation of Oxides 307
317
16 Preparation of Difunctional Compounds
Author Index 507
V
PREFACE
Since the original volume in this series by Ian and Shuyen Harrison, the goal of the Compendi-
um of Organic Synthetic Methods has been to facilitate the search for functional group transfor-
mations in the original literature of Organic chemistry. In Volume 2, difunctional compounds
were added, and this compilation was continued by Louis Hegedus and Leroy Wade for Volume
3 of the series. Professor Wade became the author for Volume and continued with Volume 5. I
4
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 re-
mains a valuable tool to the working organic chemist, allowing a quick check of the literature.
Even in the era of powerful computer searching, the Compendium allows one to "browse" for
new reactions and transformations that may be of interest in a rapid and logical manner. The
body of Organic chemistry literature is very large and the Compendium is a focused and highly
representative survey of the literature, and is offered in that context.
Compendium of Organic Synthetic Methods, Volume 12 contains both functional group trans-
formations and carbon-carbon bond-forming reactions from the literature appearing in the years
2002,2003, and 2004. The classification schemes used for Volumes 6-1 1 have been continued.
Difunctional compounds appear in Chapter 16. The experienced user of the Compendium will
require no special instructions for the use of Volume 12. Author citations and the Author Index
have been continued as in Volumes 6-1 1.
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 given below.
As I have throughout my writing career, I thank my wife, Sarah, and my son, Steven, for their
encouragement and support during this work. I also thank Dr. Darla Henderson, Michael
Forster, Jonathan Rose, Lauren Hilger, Rebekah Amos, and Angioline Loredo of Wiley for their
help in the publication of this volume,
MICHAEBL. SMITH
Department of Chemistry, University of Connecticut
55 N. Eagleville Road
Storrs. Connecticut 06269-3060
Voice phone: [phone]
Fax: [phone]
Email: [email protected]
Storrs, Connecticut
December 2008
vii
ABBREVIATIONS
Ac Acetyl
acac Acety lacetonate
AIBN azobis-isobutyronitde
Aqueous
9-Borabicyclo[3.3.l]nonylboryl
9-BBN 9-Borabicyclo[3.3. llnonane
BER Borohydride exchange resin
BINAP 2R, 3S-2,2'-bis-( dipheny1phosphino)- 1,1' -binaphthyl
Bmim 1- butyl-3-methylimidazolium
Bn benzyl
BOC tert-Butoxycarbonyl
bPY (BiPY) 2,T-Bipyridyl
Bu n-Butyl
Bz Benzoyl
"C Temperature in degrees Celsius
CAM Carboxamidomethyl
CAN Ceric ammonium nitrate (NH)2Ce(N03)6
C- Cyclo-
cat. Catalytic
\I b OCyPh
Cbz Carbobenzyloxy
Chirald
2S,3R-(+)-4-Dimethylamin1o,-2 -diphenyl-3-methylbutan-2-01
COD 1,5-Cyclooctadienyl
COT 1,3,5-Cyclooctatrienyl
CP Cyclopentadienyl
CSA Camphorsulfonic acid
CTAB Cetyltrimethylammonium bromide C 16H33NMe3+ Br-
0
4
CY (c-C6H11) Cyclohexyl
DABCO 1,4-Diazabicylco[ 2 .2.21o ctane
dba Dibenzylidene acetone
DBE 1,2-Dibromoethane BrCH2CH2Br
DBN
1,5-Diazabicyclo[4.3.O]non-5-ene
DBU
1,8-Diazabicyclo[5.4.O]undec-7-ene
DCC 1,3- Dicy clohexylcarbodiimide C-C&11-N=C=N-C-C6H11
ix
Abbreviations
X
DCE 1,2-Dichloroethane
DCM Dichloromethane
DDQ 2,3-Dichloro-5,6-dicyano1-, 4-benzoquinone
% de % Diastereomeric excess
DEA Diethy lamine
DEAD Diethylazodicarboxylate
Dibal-H Diisobutylaluminum hydride
Diphos (dppe)
1,2-bis-(Diphenylphosphino)ethane
Diphos-4 (dppb)
1,4-bis-(Diphenylphosphino)butane
DMA Dimethylacetamide
DMAP 4-Dimethylaminopyridine
DME Dimethoxy ethane MeOCH2CH20Me
13
DMF N,N’-Dimethylformamide HA N(CH3)2
dmP bis- [ 1,3-Di(p-methoxyphenyl)1-, 3-propanedionato]
dPm Dipivaloylmethanato
dPPb 1,4-bis-(Diphenylphosphino)butane Ph2P(CH2) 4PPh2
Ph2PCH2CH2PPh2
dPPe 1,2-bis-(Diphenylphosphino)ethane
dPPf bis-(Dipheny1phosphino)ferrocene
Ph2P(CH2) 3PPh2
dPPP 1,3-bis-(Diphenylphosphino)propane
dvb Diviny lbenzene
e- Electrolysis
% ee % Enantiomeric excess
EDA Ethy lenediamine H~NCH~CH~NHZ
EDTA Ethylenediaminetetraacetic acid
EE 1- Ethoxyethoxy EtO(Me)CHO-
Et Ethyl -CH2CH3
FMN Flavin mononucleotide
fod
tris-(6,6,7,7,8,8,8)-Heptafluoro-2,2-dimethyl-3,5-octanedionate
FP Cyclopentadienyl-bis-carbonylir on
FVP Flash Vacuum Pyrolysis
h Hour (hours)
hv Irradiation with light
1,5-HD 15Hexadienyl
HMPA Hexamethy lphosphoramide (Me2N)3P=O
HMPT Hexamethylphosphorus triamide (Me2N)3P
iPr Isopropyl -CH(CH3)2
LICA (LIPCA) Lithium cyclohexylisopropylamide
LDA Lithium diisopropylamide LiN(iPr)2
LHMDS Lithium hexamethyldisilazide LiN(SiMe2)z
LTMP Lithium 2,2,6,6-tetramethylpiperidide
MABR Methylaluminum
bis-(4-bromo-2,6-di-tert-butylphenoxide)
MAD bis-( 2,6-di- te rt-b uty l-4-methy1phenoxy)methyl aluminum
mCPBA meta-Chloroperoxybenzoic acid
Me Methyl -CH3
MEM P-Methoxyethoxymethyl MeOCH2CH20CH2-
Abbreviations xi
Mes Mesityl 2,4,6-tri-Me-CgH2
MOM Methoxymethyl MeOCH2-
Ms Methanesulfonyl CH3S02-
MS Molecular Sieves (3 or ,4 A)
MTM Methylthiomethyl CH3SCH2-
NAD Nicotinamide adenine dinucleotide
NADP Sodium triphosphopyridine nucleotide
Napth Naphthyl (C10Hd
NBD Norbornadiene
NBS N-Bromosuccinimide
NCS N-Chlorosuccinimide
Ni(R) Raney nickel
NIS N-Iodosuccinimide
NMP N-Methyl-2-p yrrolidinone
Oxone 2 KHSOS*KHSO~*K~SO~
Polymeric backbone
PCC Pyridinium chlorochromate
PDC Pyridinium dichromate
PEG Polyethylene glycol
Ph Phenyl
PhH Benzene
PhMe To1 u en e
Phth Phthaloyl
pic 2-Pyridinecarboxylate
Pip Piperidino
PMP 4-Methoxyphenyl
Pr n-Propyl
PY Pyridine
quant. Quantitative yield
Red-A1 [ (MeOCH2CH20)2AlHz]Na
S-BU sec-Butyl CH3CH2CH(CH3)
s-BuLi sec-Butyllithium CH&H2CH(Li)CH3
Siamyl Diisoamyl (CH3) 2CHCH(CH3)-
TADDOL 1,3-dioxolane
a,a,a’,a’-tetraaryl-4,5-dimethoxy-
TASF difluorotrimethyl silicate
tris-(Diethy1amino)sulfonium
TBAF Tetrabutylammonium fluoride n-Bu4N+ F
TBDMS tert-Butyldimethy lsilyl t-BuMe2Si
TBDPS tert-Butyldiphenylsilyl t-BuPh2Si
TBHP (t-BuOOH) tert-Butylhydroperoxide Me3 C 00 H
t-Bu tert-Butyl -C(CH3)3
TEBA Triethylbenzy lammonium Bn(Et)3N+
TEMPO Tetramethylpiperdinyloxy free radical
xii Abbreviations
TFA Trifluoroacetic acid
TFAA Trifluoroacetic anhydride
Tf (OTf) Triflate
THF Tetrahydrofuran
THP Tetrahy dropyran
TMEDA Tetramethylethylenediamine
TMG 1,1,3,3-Tetramethylguanidine
TMP
2,2,6,6-Tetramethylpiperidine
TMS Triniethy lsilyl -Si(CH3)3
TPAP tetra-n-Propylammonium perruthenate
To1 Tolyl
Tr Trityl
TRIS Triisopropylphenylsulfonyl
Ts(Tos) Tosyl = p-Toluenesulfonyl
XC Chiral auxiliary
INDEX, MONOFUNCTIONAL COMPOUNDS
Sections-heavy type
Pages-light type
'
1 '
16 31 46 61 76
Alkynes -_ 9 ~ 17 ~~ 51 ~, 67- t15-1
Carboxylic acid
derivatives
Alcohols, phenols -
'
1
Alakryyllss, mAeltdheyhleyndeess, .45 1 ........ 21110091 +~1, . 33314518 i~!~1 -4596 -~1 ..-.6767..1245 +~!, 78110955 53 9147 9 11112211016709 I11 112223325014 ~~ 212144346709 iI1I 221155554445 ~1 221166675690 1'Ij 218834 1229008 11 231085
Amides 181 ~ 211171 ~ ~ 216771 218846 ~ ~ 231068
Amines 182 I211172 1 1 1 216772 ' 1! 230187
Esters
Ethers, epxoides
1 1 i 1
Halides, sulfonates 16 0 1 2153 4306 1~ 5558 i~ 7709 1 8156 6 110902 I! 212115 II 1233034 I - 2144_75- 215650 1 217705 II 218950 ~ 230050 1 232101
Hydrides (RH)
Ketones
Nitriles i3 4453 ~1 5598 I1 7993 ' ;;o
..... ~ ...... 4 1. ....
Alkenes
Miscellaneous
1 PROTECTION 1 Blanks in the table
correspond to sections
for which no additional
Sect. Pg. examples were found in
the literature
Carboxylic acids 30A 15
Alcohols, thiols 45A 46
Aldehydes 60A 61
hides 90A 176
Amines 105A 206
Ketones 180A 279
...
Xlll