General and synthetic methods Volume 8

588 Pages·9.624 MB·English

General and Synthetic Methods
Volume 8

A Specialist Periodical Report
General and Synthetic Methods
Volume 8
A Review of the Literature Published during 1983
Senior Reporter
G. Pattenden, Deparfment of Chemistry,
University of Nottingharn
Reporters
J. M. Clough, ICI Plant Protection Division, Jealott3 MIA Berkshire
K. Cooper, Hizer Central Research, Sandwich, Kent
S. G. Davies, University of Oxford
S. C. Eyley, Fisons p.l.c., Loughborough, Leicestershire
C. R. A. Godfrey, lCl Plant Protection, Jealott's Hi14 Berksbire
P. F. Gordon, lCl Organics Division, Mancbester
L. M. Harwood, University of Oxford
D. W. Knight, University of Nottingham
T. W. Lee, University of Bristol
S. G. Lister, Wellcome Research Laboratories, Beckenham, Kent
K. E. B. Parkes, University of Nottingham
G. M. Robertson, University of Nottingham
S. E. Thomas, University of Oxford
P. Whittle, Pfizer Central Research, Sandwich, Kent
The Royal Society of Chemistry
Burlington House, London WIV OBN
ISBN 0-85186-894-0
ISSN 0141-2140
Copyright 01 986
The Royal Society of Chemistry
All Rights Reserved
No part of this book may be reproduced or transmitted
in any form or by any means-graphic, electronic,
including photocopying, recording, taping or
information storage and retrieval systems-without
written permission from the Royal Society of Chemistry
Printed in Great Britain by Adlard & Son Ltd, Dorking
Introduction
This report on General and Synthetic Methods covers the literature published
between January and December 1983.
The aim of the Reports has been to provide a summary and assessment of
reactions and methods in organic chemistry which are new (or useful variants
of existing ones) and appear sufficiently general to be useful in synthesis.
Interconversions between all the major functional groups are covered in five
chapters (Chapters 1-5), and the applications of organometallic compounds in
synthesis are treated in Chapter 6, Two further chapters deal with develop-
ments in the synthesis of saturated carbocycles (Chapter 7) and saturated
heterocycles (Chapter 8) and the final chapter provides a summary of
‘Highlights in Total Synthesis of Natural Products’. A list of reviews on
General and Synthetic Methods is collected at the end of the Report.
Future volumes in this series will be produced from camera-ready copy of
manuscripts.
July 1985 G. PATTENDEN

Cont ents
Chapter 1 Saturated and Unsaturated Hydrocarbons 1
By J. M. Clough and C. R. A. Godfrey
1 Saturated Hydrocarbons 1
2 Olefinic Hydrocarbons 6
3 Conjugated 1,3-Dienes 57
4 Non-conjugated Dienes 65
5 Allenic Hydrocarbons 69
6 Acetylenic Hydrocarbons 72
7 Enynes and Diynes 75
8 Polyenes 79
Chapter 2 Aldehydes and Ketones 84
By S. C. Eyley
1 Synthesis of Aldehydes and Ketones 84
Oxidative Methods 84
Reductive Methods 87
Methods Involving Umpolung 89
Other Methods 93
Cyclic Ketones 98
2 Synthesis of Functionalized Aldehydes and Ketones 02
Unsaturated Aldehydes and Ketones 102
a-Substituted Aldehydes and Ketones 109
Dicarbonyl Compounds 117
3 Protection and Deprotection of Aldehydes and Ketones 120
4 Reactions of Aldehydes and Ketones 123
Reactions of Enolates 123
Aldol Reactions 126
Conjugate Addition Reactions 128
Chapter 3 Carboxylic Acids and Derivatives 131
By D. W. Knight
1 Carboxylic Acids 131
General Synthesis 131
Acid Chlorides and Anhydrides 134
...
Contents
Vlll
Diacids 134
Hy droxy- acids 136
Keto-acids 138
Unsaturated Acids 139
Protection and Deprotection 142
Decarboxylation 142
2 Esters 144
Esterification 144
General Synthesis 145
Diesters 148
Hydroxy-esters 151
Keto-esters 155
Unsaturated Esters 160
Thioesters 167
3 Lactones 168
P-Lactones 168
Butyrolactones 168
a-Methylenebutyrolactones 175
Butenolides and Phthalides 177
Tetronic acids 181
Valerolactones 181
Macrolides 183
4 Carboxylic Acid Amides 185
Synthesis 185
Reactions 187
Thioamides 189
Peptide Bond Formation 190
5 Amino-acids 192
Synthesis 192
Dehydroamino-acids 194
Asymmetric Hydrogenation 196
Protection and Deprotection 196
Chapter 4 Alcohols, Halogeno-compounds, and Ethers 200
By L. M. ffarwood
1 Alcohols 200
Preparation by Addition to Alkenes 200
Preparation by Reduction of Carbonyl Compounds 204
Chemoselective Carbonyl Reductions 204
Stereoselective Carbonyl Reductions 206
Asymmetric Carbonyl Reductions 207
Enzymic Asymmetric Carbonyl Reductions 210