Table Of ContentReactivity and Structure
Concepts in Organic Chemistry
Volume 10
Editors:
Klaus Hafner Jean-Marie Lehn
Charles W. Rees P. von Rague Schleyer
Barry M. Trost Rudolf Zahradnik
liro Tsuji
Organic Synthesis
with
Palladium Compounds
S pringer-Verlag
Berlin Heidelberg New York 1980
Jiro Tsuji
Tokyo Institute ofTechno1ogy
Dept. of Chemical Engineering
O-Okayama, Meguro-Ku
Tokyo, Japan, 152
ISBN -13: 978-3-642-67477-8 e-ISBN-13 :978-3-642-67475-4
DOl: 10.10071978-3-642-67475-4
Library of Congress Cataloging in Publication Data. Tsuji, Jiro, 1927 -. Organic
synthesis with palladium compounds. (Reactivity and structure; v. 10). Biblio
graphy: p. Includes index. 1. Chemistry, Organic - Synthesis. 2. Palladium
catalysts. I. Title. II. Series. QD262.T78. 547'.2. 79-26092
This work is subject to copyright. All rights are reserved, whether the whole or
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the publisher.
© by Springer-Verlag Berlin Heidelberg 1980
Softcover reprint of the hardcover 1st edition 1980
Typesetting: Elsner & Behrens, Oftersheim
2152/3140-54 3 2 1 0
List of Editors
Professor Dr. Klaus Hafner Professor Dr. Jean-Marie Lehn
Institut flir Organische Chemie der TH Institut de Chimie
Petersenstr. 15 Universite de Strasbourg
D-6100 Darmstadt 1 , rue Blaise Pascal
B. P. 296/R8
F -67008 Strasbourg-Cedex
Professor Dr. Charles W. Rees, F. R. S. Professor Dr. Paul v. R. Schleyer
Hofmann Professor of Organic Chemistry Lehrstuhl flir Organische Chemie
Department of Chemistry der Universitat Erlangen-Niimberg
Imperial College of Science and Henkestr. 42
Technology D-8520 Erlangen
South Kensington
London, SW 2 AY
England
Professor Barry M. Trost Prof. Dr. Rudolf Zahradnik
Department of Chemistry Tschechoslowakische
The University of Wisconsin Akademie der Wissenschaften
1101 University Avenue J .-HeyrovskY-Institut flir Physikal.
Madison, Wisconsin 53706 Chemie und Elektrochemie
USA Machova 7
121 38 Praha 2
C.S.S.R.
v
Foreword
Around 30 years ago the transition metal chemistry received great impulses. In the focus
have been reactions of nickel and cobalt and herein especially their carbonyls. Also
industrial processes have been developed. When the technical oxidation of ethylene with
palladium chloride had been discovered, and a great number oflaboratory reactions,
many groups have turned towards this subject.
Apart from two important industrial processes - acetaldehyde and vinylacetate
from ethylene - a great number of conversions and catalytic reactions with palladium
compounds have been researched. Their mechanisms have been cleared up and have con
tributed to a better understanding of the complex chemistry of palladium. Last but not
least these reactions have also served for more understanding of organic transition metal
compounds and catalyses in general. Numerous conventional reactions appear today in
a different light. The effects of co-<;atalysts can be better interpreted. Relationships are
clarified, especially in the field of homogeneous catalysis, and justification for transfer
ring them in many cases to heterogeneous catalysts is given.
The extensive field of palladium catalysis is fascinating, and it is understandable
that continued success in its use in industry can be expected. It is hoped therefore that
this volume to which its author, Prof. liro Tsuji, has contributed so many fruitful ideas
and such impressive research data will motivate others in the field to continued studies
and stimulate new experiments.
Munich, October 1979 l. Smidt
Wacker-Chemie GmbH.
VI
Preface
Modern palladium chemistry developed very rapidly after an ingenious Wacker process
had been invented in 1958. In the Wacker process, acetaldehyde is produced on an in
dustrial scale from ethylene using PdCl and CuCl as catalysts. In addition to the .
2 2
Wacker-type oxidation of ole fins , many new reactions involving palladium compounds
have been discovered in the last 20 years.
Many unique reactions are possible with the use of palladium compounds as stoi
chiometric reagents as well as catalysts. One important aspect of palladium chemistry is
the application of these reactions to organic synthesis. Palladium compounds are con
venient reagents since they are usually stable and easy to handle. Toxicity is also not a
serious problem. On the other hand, palladium is a rather expensive metal with a high
atomic weight, so that stoichiometric consumption of palladium compounds is tolerable
only in few organic syntheses. Therefore, the use of palladium compounds in catalytic
amounts is the most desirable. Although many reactions have been discovered in the last
20 years, further development is expected especially in the application of unique reac
tions of palladium to organic syntheses, particularly as catalysts.
Many research papers have been published on palladium chemistry. Also a number
of review articles and books have been published treating the rapidly expanding field of
palladium chemistry from various standpoints. Now it is almost impossible to cover and
summarize all literature on palladium chemistry published in the last 20 years. This
monograph treats "organic synthesis" with palladium, but not "organic chemistry" of
palladium. The main purpose of the book is to classify a variety of organic reactions of
palladium compounds so far discovered into several types from the standpoint of organic
synthesis. I believe that the understanding of palladium chemistry will be facilitated by
proper classification of numerous reactions of palladium compounds. Stress is placed on
synthetic usefulness. In other words, reactions with wide or potential application to
organic synthesis with high yields and selectivity are treated preferentially. In this sense,
many studies on kinetic and mechanistic aspects of the reactions involving palladium
compounds are treated only when they are helpful for sufficient and rational under
standing of reactions and likely to stimulate the discovery of further synthetic applica
tions.
On the other hand, many papers on palladium chemistry have been reported by
inorganic chemists who usually have little interest in applications to organic synthesis.
These papers would not normally be read by organic chemists. However, some of these
reactions may have a high potential value, or the principle involved could be applied to
VII
Preface
organic synthesis if scrutinized from a different point of view, so some of them are
treated briefly. With few exceptions, well-established reactions such as hydrogenation
and dehydrogenation catalyzed by metallic palladium are not treated.
With some exceptions, this monograph covers literature available in Japan at the
end of 1978.
Tokyo, October 1979 Jiro Tsuji
VIII
Table of Contents
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . ................ .
II Palladium Compounds and Complexes Useful in Organic Synthesis 2
III. Oxidation Reactions with Pd2+ Compounds ..................... 4
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2. Reactions of Olefins ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
a. Introduction .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
b. Reactions of Water (Wacker Reaction) ........ . . . . . . . . . . . . . . . 6
c. Reactions of Alcohols, Phenols and Other Hydroxy Compounds . . . . .. 13
d. Reactions of Carboxylic Acids ............................ 16
e. Oxidative Carbonylation Reactions ......................... 22
f. Reactions of Aromatic Compounds .......... . . . . . . . . . . . . . .. 26
g. Reactions of Carbanions ................................ 30
h. Reactions of Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 32
i. Reactions of Hydrogen Cyanide and Chloride .................. 35
j. Oxidative Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 35
k. Reactions of Alkynes .................................. 36
3. Synthetic Reactions with 1T-Allyl Complexes ........ . . . . . . . . . . . .. 37
a. Introduction ....................................... , 37
b. Methods of Preparing 1T-Allylpalladium Complexes .......... . . . .. 37
c. Reactions of Carbon Monoxide and Isocyanides . . . . . . . . . . . . . . . .. 43
d. Reactions of Active Methylene Compounds . . . . . . . . . . . . . . . . . . .. 45
e. Reactions of Other Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . .. 50
4. Reactions of Aromatic Compounds .............. . . . . . . . . . . . .. 51
5. Synthetic Reactions by Transmetalla'tion of Organomercury Compounds
and Related Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 56
6. Synthetic Reactions Based on Chelation of Heteroatoms . . . . . . . . . . . .. 67
a. Ortho-Palladation of Aromatic Compounds. . . . . . . . . . . . . . . . . . .. 67
b. Reactions of Allylic and Homoallylic Amines and Sulfides . . . . . . . . .. 71
7. Dehydrogenation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 74
8. Reactions of Alkynes .................................... 76
IX
Table of Contents
9. Reactions of Alcohols and Carbon Monoxide. . . . . . . . . . . . . . . . . . . .. 77
10. Miscellaneous Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 79
IV. Catalytic Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 81
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 81
2. Reactions of Oletins ................................... " 81
a. Carbonylation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 81
b. Addition Reactions (Oligomerization and Co-Oligomerization) . . . . . .. 84
c. Hydrosilylation Reactions ............................... 87
d. Miscellaneous Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 88
3. Reactions of Conjugated Dienes ............................. 90
a. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 90
b. Oligomerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 91
c. Telomerization with Water, Alcohols and Phenols. . . . . . . . . . . . . . .. 93
d. Telomerization with Carboxylic Acids ................. . . . . . . 96
e. Telomerization with Ammonia and Amines . . . . . . . . . . . . . . . . . . .. 98
f. Telomerization with Enamines ......... . . . . . . . . . . . . . . . . . .. 99
g. Telomerization with Active Methylene and Methyne Compounds ..... 99
h. Reactions of Silicon Compounds . . . . . . . . . . . . . . . . . . . . . . . . . .. 101
i. Carbonylation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 104
j. Reactions ofPhenylhydrazones and Oximes ................... 105
k. Cocyc1ization Reactions. . . ............................ " 106
1. Reactions of Carbon Dioxide ............................. 108
m. Application of Butadiene Telomers to Natural Product Syntheses ..... 109
n. Dimerization and Telomerization of Isoprene and Other Dienes. . . . . .. 119
4. Reactions of Allene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 124
5. Reactions of Allyl Ethers, Esters, and Alcohols ................... 125
6. Reactions of Alkenyl Ethers and Esters. . . . . . . . . . . . . . . . . . . . . . . .. 132
7. Reactions of Organic Halides ............................... 134
a. Allylic Halides ..................................... " 134
b. Aryl Halides ........................................ 137
c. Alkenyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 146
d. Acyl Halides ........................................ 152
e. Reactions of a-Halo Ketones and Benzyl Halides ................ 156
8. Decarbonylation of Aldehydes .............................. 157
9. Reaction of Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 159
a. Carbonylation Reactions .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 159
b. Addition and Cyc1ization Reactions. . . . . . . . . . . . . • . . . . . . . . . .. 162
c. Reactions with Silicon Compounds ......................... 164
d. Miscellaneous Reaction ..... . . . . . . . . . . . . . . . . . . . . . . . . . . .. 165
10. Reactions of Silicon Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 166
11. Reactions of Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 167
12. Reactions oflsocyanides .................................. 168
13. Palladium Catalyzed Decomposition of Azo Compounds, Azides and
Peroxides ............................................ 170
x
Table of Contents
14. Rearrangement Reactions Promoted by PdC12 .••.••••••• . • • • . • • •• 173
15. Miscellaneous Reactions of Carbon Monoxide and Carbon Dioxide ...... 175
16. Reductions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 176
17. Miscellaneous Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 177
References .............................................. 179
Subject Index ............................................ 201
XI
