Ei ichi negishi, armin de meijere handbook of organopalladium chemistry for organic synthesis vol 2 wiley (2002)

HANDBOOK OFORGANOPALLADIUM CHEMISTRY FOR ORGANIC SYNTHESIS Volume 2 Edited by Ei-ichi Negishi Purdue University West Lafayette, Indiana A.. III.2.14.1 Palladium-Catalyzed -Substitution R

HANDBOOK OF

ORGANOPALLADIUM CHEMISTRY FOR ORGANIC SYNTHESIS

Volume 2

HANDBOOK OF

ORGANOPALLADIUM CHEMISTRY FOR ORGANIC SYNTHESIS

Volume 2

Edited by

Ei-ichi Negishi

Purdue University

West Lafayette, Indiana

A de Meijere, Associate Editor

Copyright © 2002 by John Wiley & Sons, Inc., New York All rights reserved.

Published simultaneously in Canada.

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10 9 8 7 6 5 4 3 2 1

Ei-ichi Negishi

Ei-ichi Negishi

IN SITU GENERATION, AND SOME PHYSICAL AND CHEMICAL

PROPERTIES

Ei-ichi Negishi

Ei-ichi Negishi

II.2.2 Palladium Complexes Containing Halogen

Ei-ichi Negishi

II.2.3 Pd(0) and Pd(II) Complexes Containing Phosphorus and Other

Dani¯ele Choueiry and Ei-ichi Negishi

II.2.4 Pd(0) and Pd(II) Complexes Containing Sulfur and Selenium

Kunio Hiroi

King Kuok (Mimi)Hii

II.2.6 Palladium Complexes Containing Metal Ligands 91

Koichiro Oshima

Masamichi Ogasawara and Tamio Hayashi

II.3.1 General Discussion of the Methods of Synthesis and in-Situ

Ei-ichi Negishi

II.3.2 Stoichiometric Synthesis and Some Notable Properties of

III.2.1 Overview of the Negishi Protocol with Zn, Al, Zr,

Ei-ichi Negishi

Akira Suzuki

Masanori Kosugi and Keigo Fugami

III.2.4 Overview of Other Palladium-Catalyzed Cross-Coupling

Tamejiro Hiyama and Eiji Shirakawa

Luigi Anastasia and Ei-ichi Negishi

III.2.6 Palladium-Catalyzed Alkenyl–Aryl, Aryl–Alkenyl, and

Shouquan Huo and Ei-ichi Negishi

III.2.7 Heteroaromatics via Palladium-Catalyzed Cross-Coupling 409

Kjell Undheim

CONTENTS vii

Kenkichi Sonogashira

III.2.8.2 Palladium-Catalyzed Alkynylation with

Alkynylmetals and Alkynyl Electrophiles 531

Ei-ichi Negishi and Carding Xu

III.2.9 Palladium-Catalyzed Cross-Coupling between Allyl,

Benzyl, or Propargyl Groups and Unsaturated Groups 551

Ei-ichi Negishi and Fang Liu

III.2.10 Palladium-Catalyzed Cross-Coupling between Allyl-,

Benzyl-, or Propargylmetals and Allyl, Benzyl,

Ei-ichi Negishi and Baiqiao Liao

III.2.11 Palladium-Catalyzed Cross-Coupling Involving

III.2.11.1 Palladium-Catalyzed Cross-Coupling

Ei-ichi Negishi and Sebastien Gagneur

III.2.11.2 Reactions between Homoallyl-,

Homopropargyl-, or Homobenzylmetals

Ei-ichi Negishi and Fanxing Zeng

III.2.12 Palladium-Catalyzed Cross-Coupling Involving

III.2.12.1 Palladium-Catalyzed Cross-Coupling with

Takumichi Sugihara

III.2.12.2 Palladium-Catalyzed Cross-Coupling

with Other -Hetero-Substituted

Takumichi Sugihara

III.2.13 Palladium-Catalyzed Cross-Coupling Involving

III.2.13.1 Palladium-Catalyzed Cross-Coupling

III.2.14.1 Palladium-Catalyzed -Substitution Reactions

of Enolates and Related Derivatives Other than the Tsuji–Trost Allylation Reaction 693

Ei-ichi Negishi

III.2.14.2 Palladium-Catalyzed Cross-Coupling

Involving -Hetero-Substituted Compounds

Ei-ichi Negishi and Asaf Alimardanov

Ei-ichi Negishi and Yves Dumond

Tamio Hayashi

III.2.17 Synthesis of Conjugated Oligomers and Polymers

III.2.17.1 Synthesis of Conjugated Oligomers for

Applications in Biological and Medicinal Areas 807

Bruce H Lipshutz

III.2.17.2 Synthesis of Conjugated Polymers

A Dieter Schlüter and Zhishan Bo

III.2.18 Synthesis of Natural Products via Palladium-Catalyzed

Ze Tan and Ei-ichi Negishi

III.2.19 Structural and Mechanistic Aspects of

Christian Amatore and Anny Jutand

III.2.20 Palladium-Catalyzed Homocoupling of Organic

Martin Kotora and Tamotsu Takahashi

Anthony O King and Robert D Larsen

III.3.2 Palladium-Catalyzed Amination of Aryl Halides and

John F Hartwig

III.3.3 Palladium-Catalyzed Synthesis of Aryl Ethers and Related

John F Hartwig

III.3.4 Palladium-Catalyzed Carbon–Metal Bond Formation

Akira Hosomi and Katsukiyo Miura

CONTENTS ix

CARBOPALLADATION

Stefan Bräse and Armin de Meijere

IV.2.1.1 Scope, Mechanism, and Other Fundamental

Aspects of the Intermolecular Heck Reaction 1133

Mats Larhed and Anders Hallberg

Stefan Bräse and Armin de Meijere

IV.2.1.3 Palladium-Catalyzed Coupling Reactions for

Matthias Beller and Alexander Zapf

IV.2.2 Intramolecular Heck Reaction

Stefan Bräse and Armin de Meijere

Gerald Dyker

Masakatsu Shibasaki and Futoshi Miyazaki

IV.2.4 Carbopalladation of Alkenes not Accompanied by

Sergei I Kozhushkov and Armin de Meijere

IV.2.5 Carbopalladation of Alkynes Followed by Trapping with

Sandro Cacchi and Giancarlo Fabrizi

IV.2.6 Carbopalladation of Alkynes Followed by Trapping

Vladimir Gevorgyan and Yoshinori Yamamoto

IV.3.1 Palladium-Catalyzed Cascade Carbopalladation:

Termination with Alkenes, Arenes, and

Stefan Bräse and Armin de Meijere

IV.3.2 Palladium-Catalyzed Cascade Carbopalladation:

Stefan Bräse and Armin de Meijere

IV.3.3 Palladium-Catalyzed Tandem and Cascade

Carbopalladation of Alkynes and 1,1-Disubstituted

Ei-ichi Negishi and Christophe Copéret

Takashi Takahashi and Takayuki Doi

Vladimir Gevorgyan

Keisuke Suzuki and Ken Ohmori

IV.6.2 Arene Substitution Involving Temporary Incorporation

and Removal of Carbon Tethers via Carbopalladation

Oliver Reiser

IV.10.1 Palladium-Catalyzed Oligomerization and

Polymerization of Dienes and Related Compounds 1579

James M Takacs

IV.10.2 Palladium-Catalyzed Benzannulation Reactions

Shinichi Saito and Yoshinori Yamamoto

IV.10.3 Other Reactions Involving Palladacyclopropanes and

Armin de Meijere and Oliver Reiser

Paul Knochel

CONTENTS xi

VOLUME 2

NUCLEOPHILIC ATTACK ON LIGANDS

Ei-ichi Negishi

V.2.1 The Tsuji–Trost Reaction and Related Carbon–Carbon

V.2.1.1 Overview of the Palladium-Catalyzed Carbon–

Carbon Bond Formation via -Allylpalladium

Jiro Tsuji

V.2.1.2 Synthetic Scope of the Tsuji-Trost Reaction with

Allylic Halides, Carboxylates, Ethers, and Related

Lara Acemoglu and Jonathan M J Williams

V.2.1.3 Palladium-Catalyzed Allylation with

Marcial Moreno-Mañas and Roser Pleixats

V.2.1.4 Palladium-Catalyzed Allylation and Related

Substitution Reactions of Enolates and Related Derivatives of “Ordinary” Ketones, Aldehydes,

Ei-ichi Negishi and Show-Yee Liou

V.2.1.5 Palladium-Catalyzed Substitution Reactions

Christine Courillon, Serge Thorimbert, and Max Malacrìa

V.2.1.6 Palladium-Catalyzed Substitution Reactions of

Sulfur and Other Heavier Group 16

Kunio Hiroi

V.2.1.7 Palladium-Catalyzed Substitution Reactions

of Nitrogen and Other Group 15 Atom-Containing

Shun-Ichi Murahashi and Yasushi Imada

V.2.1.8 Palladium-Catalyzed Substitution Reactions

Tadakatsu Mandai

V.2.1.9 Palladium-Catalyzed Reactions

of Soft Carbon Nucleophiles with Dienes,

Hiroyuki Nakamura and Yoshinori Yamamoto

V.2.2 Palladium-Catalyzed Allylic, Propargylic, and Allenic

Substitution with Nitrogen, Oxygen, and Other Groups

V.2.2.1 Palladium-Catalyzed Substitution Reactions

of Allylic, Propargylic, and Related Electrophiles

Tadakatsu Mandai

V.2.2.2 C—O and C—N Bond Formation Involving

Conjugated Dienes and Allylpalladium

Pher G Andersson and Jan-E Bäckvall

V.2.2.3 Use of Alkenes as Precursors to -Allylpalladium

Derivatives in Allylic Substitution with O, N

Björn Åkermark and Krister Zetterberg

V.2.3 Palladium-Catalyzed Allylic, Propargylic, and Allenic

Substitution with Hydrogen and Metal Nucleophiles 1887V.2.3.1 Palladium-Catalyzed Hydrogenolysis of Allyl

Katsuhiko Inomata and Hideki Kinoshita

V.2.3.2 Palladium-Catalyzed Deprotection of Allyl-Based

Mark Lipton

V.2.3.3 Palladium-Catalyzed Allylic and Related Silylation

Yasushi Tsuji

V.2.3.4 Palladium-Catalyzed Reactions of Allyl and Related

Yoshinao Tamaru

V.2.4 Palladium-Catalyzed Asymmetric Allylation

Lara Acemoglu and Jonathan M J Williams

V.2.5 Other Reactions of Allylpalladium and Related Derivatives 1981V.2.5.1 Elimination of Allylpalladium

Isao Shimizu

V.2.5.2 Cycloaddition Reactions of Allylpalladium

Sensuke Ogoshi

CONTENTS xiii

V.2.5.3 Rearrangements of Allylpalladium

Pavel Kocˇovsk´y and Ivo Star´y

V.2.6 Synthesis of Natural Products and Biologically Active

Compounds via Allylpalladium and Related Derivatives 2027

Véronique Michelet, Jean-Pierre Genêt, and Monique Savignac

V.3.1 The Wacker Oxidation and Related Intermolecular Reactions

Involving Oxygen and Other Group 16 Atom Nucleophiles 2119V.3.1.1 The Wacker Oxidation and Related

Patrick M Henry

V.3.1.2 Other Intermolecular Oxypalladation–

Takahiro Hosokawa and Shun-Ichi Murahashi

V.3.1.3 Intermolecular Oxypalladation not Accompanied

Takahiro Hosokawa and Shun-Ichi Murahashi

V.3.2 Intramolecular Oxypalladation and Related Reactions

V.3.2.1 Oxypalladation–Dehydropalladation Tandem

Takahiro Hosokawa and Shun-Ichi Murahashi

V.3.2.2 Oxypalladation–Reductive Elimination

Domino Reactions with Organopalladium

Sandro Cacchi and Antonio Arcadi

V.3.3 Aminopalladation and Related Reactions Involving Other

V.3.3.1 Aminopalladation–Dehydropalladation

Takahiro Hosokawa

V.3.3.2 Aminopalladation–Reductive Elimination Domino

Reactions with Organopalladium Derivatives 2227

Sandro Cacchi and Fabio Marinelli

V.3.4 Palladium-Catalyzed Reactions Involving Attack on

Palladium–Alkene, Palladium–Alkyne, and Related

Geneviève Balme, Didier Bouyssi, and Nuno Monteiro

V.3.5 Palladium-Catalyzed Reactions via Halopalladation

Xiyan Lu

V.3.6 Synthesis of Natural Products via Nucleophilic Attack

on -Ligands of Palladium–Alkene, Palladium–Alkyne,

Caiding Xu and Ei-ichi Negishi

RELATED REACTIONS INVOLVING MIGRATORY INSERTION

Ei-ichi Negishi

and Alkynylpalladium Derivatives Involving Carbon Monoxide

VI.2.1 Reactions of Acylpalladium Derivatives with Oxygen,

Nitrogen, and Other Group 15, 16, and 17 Atom Nucleophiles 2313

VI.2.1.1.1 Palladium-Catalyzed Carbonylation

Miwako Mori

VI.2.1.1.2 Palladium-Catalyzed

Hydrocarbo-xylation and Related Carbonylation Reactions of -Bonded Compounds 2333

Bassam El Ali and Howard Alper

VI.2.1.2 Intramolecular Cyclization Processes

via Palladium-Catalyzed Carbonylative

Vittorio Farina and Magnus Eriksson

VI.2.1.3 Tandem and Cascade Processes Terminated

by Carbonylative Esterification, Amidation,

Hans-Günther Schmalz and Oliver Geis

VI.2.1.4 Palladium-Catalyzed Double

Yong-Shou Lin and Akio Yamamoto

VI.2.2 Reactions of Acylpalladium Derivatives with Organometals

Yoshinao Tamaru and Masanari Kimura

CONTENTS xv

VI.2.3 Reactions of Acylpalladium Derivatives with Enolates

Ei-ichi Negishi and Hidefumi Makabe

VI.2.4 Synthesis of Aldehydes via Hydrogenolysis

Robert D Larsen and Anthony O King

and Allenylpalladium Derivatives Involving Carbon Monoxide

Tadakatsu Mandai

VI.4.1.1 Intramolecular Acylpalladation Reactions with

Alkenes, Alkynes, and Related Unsaturated Compounds 2519

Christophe Copéret and Ei-ichi Negishi

VI.4.1.2 Intramolecular Acylpalladation with Arenes 2553

Youichi Ishii and Masanobu Hidai

Giambattista Consiglio

Christophe Copéret

VI.4.4 Carbonylation of Alkenes and Alkynes Initiated by

VI.4.4.1 Carbonylation Processes Not Involving CO

Gian Paolo Chiusoli and Mirco Costa

Bartolo Gabriele and Giuseppe Salerno

VI.5.1 Palladium-Catalyzed Decarbonylation

Jiro Tsuji

VI.5.2 Formation and Reactions of Ketenes Generated

Hiroshi Okumoto

Miwako Mori

VI.7 Palladium-Catalyzed Carbonylative Oxidation 2683

VI.7.1 Palladium-Catalyzed Carbonylative Oxidation of Arenes,

Yuzo Fujiwara and Chengguo Jia

VI.7.2 Palladium-Catalyzed Carbonylative Oxidation

Other than Those Involving Migratory Insertion 2691

Shin-ichiro Uchiumi and Kikuo Ataka

Yoshihiko Ito and Michinori Suginome

PALLADIUM-CATALYZED REACTIONS VIA HYDROPALLADATION,

METALLOPALLADATION, AND OTHER RELATED SYN

ADDITION REACTIONS WITHOUT CARBON–CARBON BOND

FORMATION OR CLEAVAGE

Ei-ichi Negishi

VII.2.1 Palladium-Catalyzed Heterogeneous

Anthony O King, Robert D Larsen, and Ei-ichi Negishi

VII.2.2 Palladium-Catalyzed Homogeneous

VII.2.2.1 Palladium-Catalyzed Homogeneous

Hydrogenation with Dihydrogen and

Ariel Haskel and Ehud Keinan

Ei-ichi Negishi

CONTENTS xvii

Koichiro Oshima

Akiya Ogawa

HAVE NOT BEEN DISCUSSED IN EARLIER PARTS

Ei-ichi Negishi

VIII.2.1 Homodimerization of Hydrocarbons via

Yuzo Fujiwara and Chengguo Jia

VIII.2.2 Palladium-Promoted Alkene-Arene Coupling

Yuzo Fujiwara

VIII.3.1 Oxidation of Silyl Enol Ethers and Related

Enol Derivatives to ,-Unsaturated Enones

Yoshihiko Ito and Michinori Suginome

VIII.3.2 Oxidation of Amines, Alcohols,

Shun-Ichi Murahashi and Naruyoshi Komiya

VIII.3.3 Other Palladium-Catalyzed or -Promoted

Oxidation Reactions via 1,2- or 1,4-Elimination 2895

Yuzo Fujiwara and Ei-ichi Negishi

Ei-ichi Negishi

REACTIONS CATALYZED BY PALLADIUM

IX.2 Rearrangement Reactions Catalyzed by Palladium 2919

IX.2.1 Palladium-Catalyzed Carbon Skeletal Rearrangements 2919

IX.2.1.1 Cope, Claisen, and Other [3,3] Rearrangements 2919

Hiroyuki Nakamura and Yoshinori Yamamoto

IX.2.1.2 Palladium-Catalyzed Carbon Skeletal

Rearrange-ments Other than [3, 3] RearrangeRearrange-ments 2935

Ei-ichi Negishi

IX.2.2 Palladium-Catalyzed Rearrangements of Oxygen Functions 2939

Masaaki Suzuki, Takamitsu Hosoya, and Ryoji Noyori

CHEMISTRY

Irina P Beletskaya and Andrei V Cheprakov

Tony Y Zhang

Stefan Bräse, Johannes Köbberling, and Nils Griebenow

Ei-ichi Negishi

Ei-ichi Negishi

Ei-ichi Negishi and Fang Liu

Organic compounds mostly consist of just ten to a dozen non-metallic elements including

C, H, N, P, O, S, and halogens This may be one of the main reasons why chemists, untilrelatively recently, tended to rely heavily on those reactions involving only non-metallicelements Many of them including the Diels-Alder reaction, the Claisen and Cope re-arrangements continue to be important Even so, their combined synthetic scope has beenrather limited

Regardless of how one defines metallic elements, more than three quarters of theelements may be considered to be metals It is therefore not surprising that some of them,mostly main group metals such as Li, Na, K, and Mg, have been used as reagents orcomponents of reagents for many decades primarily for generating carbanionic and otheranionic species Some other main group metals, such as Al and B, have also been used formany years primarily as components of Lewis acid catalysts in the Friedel-Crafts andother acid-catalyzed reactions The significance of metal’s ability to readily provide low-lying empty orbitals has become gradually but widely recognized and led to the develop-ment of a modern synthetic methodology involving B, Al, and other predominantlyLewis-acidic main group metals

Some d-block transition metals (transition metals hereafter) including Ni, Pd, Pt, Rh,

Ru, and so on have long been used as catalysts or catalyst components for hydrogenationand other reductions, while some others, such as Cr and Mn, have been used in stoichio-metric oxidation reactions Even some transition metal-catalyzed C! C bond-formingreactions, such as Roelen’s oxo process was discovered as early as 1938 However, it wasnot until the 1950s that the full synthetic potential of transition metals began to be recog-nized The discovery and development of the Ziegler-Natta polymerization indicated theability of some early transition metals, such as Ti and Zr, to serve as superior catalysts forC! C bond formation Development of the Dewar-Chatt-Duncanson synergistic bondingscheme provided a theoretical foundation for the “carbenoidal” characteristic of transition

metals, as discussed in Sect II.3.1 The discovery of ferrocene in 1951 and the

subse-quent clarification of its structure triggered systematic investigations that have madeavailable a wide range of metallocene and related transition metal complexes for reagentsand catalysts In the area of organopalladium chemistry, it is widely agreed that invention

of the Wacker oxidation in 1959 may have marked the beginning of the modern

Pd-catalyzed organic synthesis (Sect I.1)

Over the last thirty to forty years, compounds containing roughly ten to a dozen sition metals have been shown to serve as versatile and useful catalysts in organic syn-thesis Today, they collectively represent the third major class of catalysts, enzymes andnon-transition metal acids and bases being the other two Of various factors, the follow-ing two appear to be critically responsible for rendering them superior catalysts and cat-alyst components One is their ability to provide readily and simultaneously both fillednonbonding and low-lying empty orbitals Together, they provide effective frontier or-bitals, namely HOMO and LUMO, for concerted and synergistic interactions leading to

tran-low energy-barrier transformations The other is their ability to undergo simultaneouslyand reversibly both oxidation and reduction under one set of reaction conditions.

Then, why Pd? This is a very interesting but rather difficult question Nonetheless, an

attempt to answer this question is made in Sect I.2, and the generalization summarized in Table 2 of Sect I.2 is further supported by the experimental results presented throughout

this Handbook In short, Pd simultaneously displays wide-ranging reactivity and highstereo-, regio-, and chemo-selectivities Its complexes are, in many respects, highly reac-tive And yet, they are stable enough to be used as recyclable reagents and intermediates

in catalytic processes These mysteriously favorable characteristics appear to be reservedfor just a few late second-row transition metals including Pd, Rh, and Ru that offer acombination of (i) moderately large atomic size and (ii) relatively high electronegativity,both of which render these elements very “soft”, in addition to (iii) ready and simultane-ous availability of both filled nonbonding and empty valence-shell orbitals and (iv) readyand reversible availability of two oxidation states separated by two elections mentionedabove The general lack of serious toxicity problems and ease of handling, which may notrequire rigorous exclusion of air and moisture in many cases are two additional factorsassociated with them

The versatility of Pd is very well indicated by the contents of this Handbook listingnearly 150 authored sections spread over ten parts This Handbook cannot and does notlist all examples of the organopalladium reactions However, efforts have been made toconsider all conceivable Pd-catalyzed organic transformations and discuss all knownones, even though it was necessary to omit about ten topics for various unfortunatereasons

Part I discusses the historical background of organopalladium chemistry (Sect I.1) as

well as the fundamental properties and patterns of the reactions of Pd and its complexes

(Sect I.2) In Part II, generation and preparation of Pd complexes are discussed These

discussions are rather brief, as the main focus of this Handbook is placed on Pd-catalyzedorganic transformations

In some of the previously published books on organopalladium chemistry, topics areclassified according to the organic starting compounds This may be a useful and readilymanageable classification from the organometallic viewpoint However, it is envisionedthat the prospective readers and users of this Handbook are mostly synthetic organicchemists who are primarily interested in knowing how the organic compounds of theirinterest might be best prepared by using Pd complexes as catalysts This perspective, how-ever, does not readily lend itself to an attractive and satisfactory means of classifying theorganopalladium chemistry For both synthetic organic chemists and those who wish tolearn more about the organopalladium chemistry from a more organometallic perspective,

it appears best to classify the organopalladium chemistry according to some basic patterns

of organometallic transformations representing the starting compound!product

relation-ships As discussed in Sect I.2, formation of carbon!carbon and/or carbon!heteroatom

bonds through the use of organotransition metals can be mostly achieved via the followingfour processes: (i) reductive elimination, (ii) carbometallation, (iii) nucleophilic or elec-trophilic attack on ligands, and (iv) migratory insertion As a versatile transition metal, Pdhas been shown to participate in them all

Thus, in Part III, the Pd-catalyzed coupling including the carbon-carbon

cross-coupling represented by the Negishi, Stille, and Suzuki protocols as well as the

Sono-gashira alkynylation (Sect III.2) and the more recently developed carbon-heteroatom coupling reactions (Sect III.3) are presented In most of these reactions, reductive

elimination is believed to be a critical step This is followed by Part IV in which a tematic discussion of carbopalladation represented by the Heck reaction (Sect IV.2) is

sys-presented The scope of carbopalladation, however, extends far beyond that of the Heck

reaction, and these other topics are discussed in Sects IV.3–IV.11 There are two major

topics that pertain to nucleophilic attack on ligands of organopalladium complexes

discussed in Part V One is the Tsuji-Trost reaction This and related reactions of allylpalladium derivatives are discussed in Sect V.2 The other is the Wacker oxidation.

This and related reactions involving Pd-complexes are discussed in Sect V.3 In Part

VI, carbonylation and other migratory insertion reactions of organopalladium pounds are discussed In Parts III–VI, the significance of applications of the above- mentioned reactions to the synthesis of natural products (Sects III.2.17.1, III.2.18, IV.8, V.2.6, V.3.6, and VI.6) and polymers of material chemical interest (Sects III.2.17.2, VI.4.2, and VI.8) are recognized and discussed in the sections shown in

Despite the high propensity to undergo concerted reactions, organopalladium derivatives

can also serve as sources of carbocationic species as indicated in Part V In some cases,

this can lead to skeletal rearrangements similar to the pinacol-pinacolone rearrangement

Other more concerted rearrangements are also observable, as discussed in Part IX These

reactions add extra dimensions to the diverse chemistry of organaopalladium compounds.Lastly, some significant technological developments including aqueous palladium cataly-

sis (Sect X.1), immobilized Pd catalysts (Sect X.2) and combinatorial organopalladium chemistry (Sect X.3) are making organopalladium chemistry even more important and

useful in organic synthesis

Looking back, it all started when one of my senior colleagues, Professor H Feuer, peatedly visited my office several years ago to persuade me to write a book for VCH andlater Wiley Despite my initial firm determination not to write any book, a notion ofpreparing this Handbook on a topic that has occupied a significant part of my own re-search career grew in my mind, and I was finally persuaded by him and Dr BarbaraGoldman of Wiley My life-long mentor and a 1979 Nobel Prize winner, Professor H C.Brown, has directly and indirectly influenced and encouraged me throughout my career,including this Handbook writing I wish to dedicate my own contributions to these twosenior colleagues at Purdue I should also like to acknowledge that, through the generos-ity of Professor and Mrs Brown, the Herbert C Brown Distinguished Professorship wasestablished in 1999, of which I have been the very fortunate inaugural appointee This hashad many favorable influences on my involvement in this Handbook preparation In thisand other connections, I am very thankful to my colleagues in the Chemistry Department,especially Dean H A Morrison and former Head R A Walton

re-The actual overall and detailed layout of the Handbook was finalized during my month stay in Göttingen, Germany, as an Alexandar von Humboldt Senior ResearcherAwardee during the summer of 1998 My German host and Associate Editor of theHandbook, Professor A de Meijere has not only enthusiastically supported my plan butalso heavily contributed to the Handbook both as an author and as a member of theeditorial board I am also deeply indebted to the other eight editorial board members,

namely Professors J E Bäckvall, S Cacchi, T Hayashi, Y Ito, M Kosugi, S I hashi, K Oshima, and Y Yamamoto They all have contributed one or more sections andsacrificed their extremely precious time in the editorial phase In fact, the ten editorialboard members have authored and coauthored nearly one half of all sections.

Mura-It is nonetheless unmistakably clear that this Handbook is a joint production by a munity or group of 141 chemists and that the great majority of writing and drawing workshave actually been performed by the 131 contributors whom I sincerely thank on behalf ofthe editorial board including myself Without their massive contributions and cooperation,

com-it would have been absolutely impossible to publish a book of this magncom-itude It is myparticular pleasure to note that no less than 21 current and former associates of my ownresearch group have made their massive contributions and enthusiastically supported myactivities They are, in the order of appearance, D Choueiry, L Anastasia, S Huo, C Xu,

F Liu, B Liao, S Gagneur, F Zeng, T Sugihara, K Takagi, F T Luo, A Alimardanov,

Y Dumond, Z Tan, M Kotora, T(amotsu) Takahashi, A O King, C Coperet, S Ma,

S Y Liou, and H Makabe

While I must refrain from mentioning the names of the other 110 contributors, most ofthem are indeed my long-time colleagues and friends, to whom I deeply thank for theircollaborations and contributions I have also greatly appreciated and enjoyed collabora-tions with my new colleagues, some of whom I have not yet met Many of my other es-teemed colleagues were too busy to participate in the project Some of them neverthelessmade valuable suggestions that have been very useful in the planning stage

Typing and a significant part of drawing of our own manuscripts and, more tantly, a seemingly infinite number of correspondences as well as a myriad of other Hand-book-related jobs have been handled by Ms M Coree (through 2000) and Ms LyndaFaiola (since 2001) The preparation of this extensive Handbook would not have beenpossible without their dedicated work for which I am deeply thankful Many direct andindirect assistances made by my wife, Sumire, and other members of my family are alsothankfully acknowledged

impor-Last but not least, I thank editorial staff members of Wiley, including compositors andfreelancers, especially Dr Barbara Goldman in the initial phase, Dr Darla Henderson,Amy Romano, and Christine Punzo for their interest, encouragement, and collaboration

seriously outdated sections may be revised and published as supplementary volumes atappropriate times In this regard, I have already received oral consents from more than adozen colleagues, and I am currently seeking a dozen or so additional collaborators.

Ei-ichi Negishi

Herbert C Brown Distinguished Professor of Chemistry

Purdue University, West Lafayette, Indiana

PREFACE xxiii

CHRISTIANAMATORE, Departement de Chimie, École Normale Superieure, UMR CNRS

8640, 24 Rue Lhomond 75231 Paris, Cedex 05, France

LUIGI ANASTASIA, Herbert C Brown Laboratories of Chemistry, Purdue University,West Lafayette, Indiana 47907-1393, USA

PHERG ANDERSSON, Department of Organic Chemistry, Arrhenius Laboratory, StockholmUniversity, SE 106 91 Stockholm, Sweden

ANTONIOARCADI, Dipartimento di Chimica Ingegneria Chimica e Materiali della Facolta

di Scienze, Universita de L’Aquila Via Vetoio, Coppito Due, I-67100 L’Aquila, Italy

KIKUO ATAKA, UBE Industries, Ltd., UBE Research Institute, 1978-5 Kogushi, Ube,Yamaguchi, 755-8633 Japan

JAN-E BÄCKVALL, Department of Organic Chemistry, Arrhenius Laboratory, StockholmUniversity, SE-106 91 Stockholm, Sweden

GENEVIÈVEBALME, Laboratoire de Chimie Organique 1, UMR 5622 du CNRS, site Claude Bernard Lyon 1, Bâtiment 308, 43 Bd du 11 Novembre 1918, 69622Villeurbanne Cédex, France

Univer-IRINA P BELETSKAYA, Laboratory of Elementoorganic Compounds, Department ofChemistry, Moscow State University, Moscow, 119899, Russia

MATTHIAS BELLER, Institut für Organische Katalyseforschung an der UniversitätRostock e.V., Buchbinderstr 5-6, Rostock, Germany 18055

ZHISHAN BO, Freie Universität Berlin, Institut für Organische Chemie, Takustr 3, D-14195 Berlin, Germany

DIDIERBOUYSSI, Laboratoire de Chimie Organique 1, U.M.R 5622 du CNRS, site Claude Bernard Lyon 1, Bâtiment 308, 43 Bd du 11 Novembre 1918, 69622Villeurbanne Cédex, France

Univer-STEFANBRÄSE, Kekule-Institut für Organische Chemie und Biochemie der Rheinischen,Friedrich-Wilhelms-Universitat Bonn, Gerhard-Domagk-Strasse 1, D-53121 Bonn,Germany.

SANDRO CACCHI, Dipartimento di Studi di Chimica e Tecnologia, delle SostanzeBiologicamente Attive, Universita degli Studi “La Sapienza,” P le A Moro, 5, I-00185Rome, Italy

ALLANJ CANTY, School of Chemistry, University of Tasmania, Hobart and Launceston,Tasmania, Australia 7001

MARTA CATELLANI, Dipartimento di Chimica Organica e Industriale, Università degliStudi di Parma, Parco Area delle Scienze, 17/A, 43100 Parma, Italy

ANDREI V CHEPRAKOV, Laboratory of Elementoorganic Compounds, Department ofChemistry, Moscow State University, 119899 Moscow, Russia

GIAN PAOLO CHIUSOLI, Dipartimento di Chimica Organica e Industriale, UniversitàDegli Studi di Parma, Parco Area delle Scienze 17/A, I-43100 Parma, Italy

DANIÈLE CHOUEIRY, Lilly Development Centre SA, Parc Scientifique de la-Neuve, Rue Granbonpré 11, B-1348 Mont-Saint-Guibert, Belgium

Louvain-GIAMBATTISTA CONSIGLIO, Laboratorium für Technische Chemie, ETH-Zentrum sitätstrasse 6, CH-8092 Zürich, Switzerland

Univer-CHRISTOPHECOPÉRET, Laboratoire de Chimie, Organometallique de Surface, UMR 9986CNRS-ESCPE Lyon, Bât F308, 43 Bd du 11 Novembre 1918, F-69616 Villeurbanne,France

MIRCOCOSTA, Dipartimento di Chimica Organica e Industriale, Università Degli Studi

di Parma, Parco Area delle Scienze 17/A, I-43100 Parma, Italy

CHRISTINE COURILLON, Universite Pierre et Marie Curie (Paris VI), Laboratoire deChimie Organique de Synthèse, Case 229, T.44, 2ET, 4 Place Jussieu, 75252 Paris,Cedex 05, France

ARMIN DE MEIJERE, Institut für Organische Chemie, Georg-August-Universität,Tammanstrasse 2, D-37077 Göttingen, Germany

TAKAYUKI DOI, Department of Applied Chemistry, Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo, 152-8552, Japan

YVESDUMOND, Roche Vitamins Ltd VFCR Department, Bldg 214, Room 0.62,

VITTORIOFARINA, Chemical Development, Boehringer Ingelheim Pharmaceuticals Inc.,

900 Ridgebury Road, Ridgefield, Connecticut 06877-0368, USA

KEIGO FUGAMI, Department of Chemistry, Faculty of Engineering, Gunma University, 1-5-1 Tenjin-cho, Kiryu, Gunma, 376-8515, Japan

YUZOFUJIWARA, 2-28-22 Tajima, Jyonanku, Fukuoka 814-0113, Japan

BARTOLOGABRIELE, Dipartimento di Scienze Farmaceutiche, Università della Calabria,

87036 Arcavacata di Rende, Cosenza, Italy

SEBASTIEN GAGNEUR, BASF Aktiengesellschaft, Functional Materials, ZDF/O-J 550,

et Marie Curie, 75231, Paris, Cedex 05, France

VLADIMIRGEVORGYAN, Department of Chemistry, University of Illinois at Chicago, 845West Taylor Street, Chicago, Illinois, 60607-7061, USA

NILS GRIEBENOW, Zentrale Forschung/Wirkstofforschung, Gebäude Q18, D-51368Leverkusen, Germany

ANDERSHALLBERG, Department of Organic Pharmaceutical Chemistry, BMC, UppsalaUniversity, SE-751 23 Uppsala, Sweden

JOHN F HARTWIG, Department of Chemistry, Yale University, 350 Edwards, NewHaven, Connecticut 06520-8107, USA

ARIEL HASKEL, Department of Chemistry, Massachusetts Institute of Technology,

77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA

TAMIO HAYASHI, Department of Chemistry, Faculty of Science, Kyoto University,Sakyo, Kyoto 606-8502, Japan

PATRICK M HENRY, Department of Chemistry, Loyola University of Chicago, 6525North Sheridan Road, Chicago, Illinois, 60626, USA

MASANOBUHIDAI, Department of Materials Science and Technology, Faculty of trial Science and Technology, Science University of Tokyo, 2641 Yamazaki, Noda,Chiba, 278-8510, Japan

Indus-KINGKUOK(MIMI) HII, King’s College London, Chemistry Department, Strand WC2R2LS London, United Kingdom

KUNIOHIROI, Department of Synthetic Organic Chemistry, Tohoku Pharmaceutical versity, 4-4-1 Komatsushima, Aoba-ku, Sendai, Miyagi, 981-8558, Japan

Uni-TAMEJIRO HIYAMA, Division of Material Chemistry, Graduate School of Engineering,Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8501, Japan

TAKAHIRO HOSOKAWA, Department of Environmental Systems Engineering, KochiUniversity of Technology, Tosayamada, Kochi, 782-8502, Japan

AKIRA HOSOMI, Department of Chemistry, Graduate School of Pure and AppliedSciences, University of Tsukuba, Tsukuba, Ibaraki, 305-8571, Japan.

TAKAMITSU HOSOYA, Department of Biomolecular Science, Faculty of Engineering,Gifu University, Yanagido, Gifu, 501-1193, Japan

SHOUQUANHUO, Herbert C Brown Laboratories of Chemistry, Purdue University, WestLafayette, Indiana, 47907-1393, USA

YASUSHI IMADA, Department of Chemistry, Graduate School of Engineering Science,Osaka University, Machikaneyama 1-3, Toyonaka, Osaka, 560-8531, Japan

KATSUHIKOINOMATA, Department of Chemistry, Faculty of Science, Kanazawa sity, Kakuma, Kanazawa Ishikawa, 920-1192, Japan

Univer-YOUICHIISHII, Department of Chemistry and Biotechnology, Graduate School of neering, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan

Engi-YOSHIHIKOITO, Department of Synthetic Chemistry and Biological Chemistry, GraduateSchool of Engineering, Kyoto University, Sakyo-ku, Kyoto, 606-8501, Japan

CHENGGUOJIA, Department of Chemistry, University of Waterloo 200 University Ave.,

PAUL KNOCHEL, Institut für Organische Chemie, Ludwig-Maximilians-Universität, Butenandstrr 5-13, D-81377 München, Germany

JOHANNES KÖBBERLING, Institut für Organische Chemie, RWTH Aachen, Pirlet-Strafe 1, D-52074 Aachen, Germany

Professor-PAVEL KOCˇOVSKY´, Department of Chemistry, University of Glasgow, Glasgow, G128QQ, United Kingdom

NARUYOSHIKOMIYA, Department of Chemistry, Graduate School of Engineering Science,Osaka University, Machikaneyama 1-3, Toyonaka, Osaka, 560-8531, Japan

MASANORI KOSUGI, Department of Chemistry, Gunma University, Kiryu, Gunma, 376-8515, Japan

MARTINKOTORA, Department of Organic and Nuclear Chemistry, Faculty of Science,Charles University, Hlavova 8, 12840 Praha 2 Czech Republic

xxviii CONTRIBUTORS

SERGEII KOZHUSHKOV, Institut für Organische Chemie, der Georg-August-Universität,Tammanstrasse 2 D-37077 Göttingen, Germany.

MATSLARHED, Department of Organic Pharmaceutical Chemistry, Uppsala University,SE-751 23 Uppsala, Sweden

ROBERTD LARSEN, Dept of Process Research, 126 E Lincoln Ave, Merck & Co., Inc.,Rahway, New Jersey, 07065, USA

BAIQIAOLIAO, c/o Mr Xiao Mu Zheng 6969 Richfield Dr Reynoldsburg, Ohio, 43068,USA

YONG-SHOU LIN, Materials R&D, E-One Moli Energy (Canada) Ltd., 20,000 StewartCrescent, Maple Ridge, British Columbia, Canada V2X 9E7

JAMEST LINK, Abbott Laboratories, 100 Abbott Park Road, Abbott Park, Illinois,

FANGLIU, 795 Brunsdorph Rd Fairlawn, Ohio 44333 USA

XIYANLU, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354Fenglin Lu, Shanghai, 200032, China

FEN-TAIRLUO, Institute of Chemistry, Academia Sinica, 128 Academia Road, Section 2,Nankang, Taipei, Taiwan 11529

SHENGMING MA, Shanghai Institute of Organic Chemistry, Chinese Academy ofSciences, 354 Fenglin Lu, Shanghai, 200032, Peoples Republic of China

HIDEFUMIMAKABE, Department of Bioscience and Biotechnology, Shinshu University,

8304 Minamiminowa Kamiina, Nagano, 399-4598, Japan

MAX MALACRÌA, Universite Pierre et Marie Curie (Paris VI), Laboratoire de ChimieOrganique de Synthèse, 75252 Paris, Cedex 05, France

TADAKATSUMANDAI, Department of Chemistry and Bioscience, Kurashiki University ofScience and the Arts, 2640 Nishinoura, Tsurajima, Kurashiki, 712-8505, Japan

FABIO MARINELLI, Dipartimento di Chimica Ingegneria Chimica e Materiali dellaFacolta di Scienze, Universita de L’Aquila, Via Vetoio, Coppito Due, I-67100L’Aquila, Italy

VÉRONIQUEMICHELET, École Nationale Superieure de Chimie de Paris, Laboratoire deSynthèse Sélective Organique et Produits Naturels, UMR C.N.R.S 7573, 11, ruePierre et Marie Curie, 75231 Paris, Cedex 05, France

KATSUKIYO MIURA, Department of Chemistry, Graduate School of Pure and AppliedSciences, University of Tsukuba, Tsukuba, Ibaraki, 305-8571, Japan

FUTOSHIMIYAZAKI, Elsai Co., Ltd., 1–3, Tokodai 5-chome, Tsukubashi, Ibaraki, 300-2635Japan.

NUNOMONTEIRO, Laboratoire de Chimie Organique 1, Universite Claude Bernard Lyon

1, 69622, Villeurbanne Cédex, France

MARCIAL MORENO-MAÑAS, Department of Chemistry, Universitat Autònoma deBarcelona, Edifici C, 08193 Cerdanyola (Barcelona), Spain

MIWAKO MORI, Graduate School of Pharmaceutical Sciences, Hokkaido University,Sapporo, 060-0812, Japan

SHUN-ICHI MURAHASHI, Department of Applied Chemistry, Okayama University ofScience, Ridai-cho 1-1 Okayama, 700-0005, Japan

HIROYUKI NAKAMURA, Department of Chemistry, Graduate School of Science, TohokuUniversity, Sendai, 980-8578, Japan

EI-ICHINEGISHI, Herbert C Brown Laboratories of Chemistry, Purdue University, WestLafayette, Indiana, 47907-1393, USA

RYOJI NOYORI, Department of Chemistry, Faculty of Science, Nagoya University,Chikusa, Nagoya, 464, Japan

MASAMICHIOGASAWARA, Department of Chemistry, Graduate School of Science, KyotoUniversity, Sakyo, Kyoto, 606-8502, Japan

AKIYA OGAWA, Department of Chemistry, Faculty of Science, Nara Women’s sity, Kitauoyanishi-machi, Nara, 630-8506, Japan

Univer-SENSUKE OGOSHI, Department of Applied Chemistry, Faculty of Engineering, OsakaUniversity, Suita, Osaka, 565-0871, Japan

KEN OHMORI, Department of Chemistry, Tokyo Institute of Technology, 2-12-1, O-okayama, Meguro-ku, Tokyo, 152-8551, Japan

HIROSHI OKUMOTO, Department of Chemistry and Bioscience, Kurashiki University ofScience and the Arts, 2640 Nishinoura Tsurajima, Kurashiki, 712-8505, Japan

KOICHIROOSHIMA, Department of Material Chemistry, Graduate School of Engineering,Kyoto University, Sakyo, Kyoto, 606-8501 Japan

ROSERPLEIXATS, Department of Chemistry, Universitat Autònoma de Barcelona, Edifici

C, 08193 Cerdanyola (Barcelona), Spain

OLIVERREISER, Universität Regensburg, Institut für Organische Chemie, Universitätsstr

Arcava-FUMIESATO, Department of Biomolecular Engineering, Tokyo Institute of Technology,

4259 Nagatsuta-cho, Midori-ku, Yokohama, 226-8501, Japan

MONIQUE SAVIGNAC, École Nationale Superieure de Chimie de Paris, Laboratoire deSynthèse Sélective Organique et Produits Naturels, UMR C.N.R.S 7573, 11 ruePierre et Marie Curie, 75231 Paris, Cedex 05, France.

A DIETERSCHLÜTER, Freie Universität Berlin, Institut für Chemie/Organische Chemie,Takustrasse 3, D-14195 Berlin, Germany

HANS-GÜNTHERSCHMALZ, Institute of Organic Chemistry, University zu Koeln, strasse 4, D-50939 Koeln, Germany

Grein-MASAKATSU SHIBASAKI, Faculty of Pharmaceutical Science, University of Tokyo,Hongo, Bunkyo-ku, Tokyo, 113-003, Japan

ISAO SHIMIZU, Department of Applied Chemistry, School of Science & Engineering,Waseda University, Okuba 3-4-1, Shinjuku, Tokyo, 169-8555, Japan

EIJI SHIRAKAWA, Graduate School of Materials Science, Japan Advanced Institute ofScience and Technology, Asahidai, Tatsunokuchi, Ishikawa, 923-1292, Japan

KENKICHI SONOGASHIRA, Department of Applied Science and Chemistry, Faculty ofEngineering, Fukui University of Technology, 3-6-1, Gakuen, Fukui, 910-8505,Japan

IVO STARY´, Institute of Organic Chemistry and Biochemistry, Academy of Sciences ofthe Czech Republic, Flemingovo 2, 16610 Prague 6, Czech Republic

TAKUMICHI SUGIHARA, Faculty of Pharmaceutical Sciences, Tokushima Bunri sity, Yamashiro-cho Tokushima, 770-8514, Japan

Univer-MICHINORI SUGINOME, Department of Synthetic Chemistry and Biological Chemistry,Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto, 606-8501, Japan

AKIRA SUZUKI, Department of Chemical Technology, Kurashiki University of Scienceand the Arts, Kurashiki, 712-8505, Japan

KEISUKESUZUKI, Department of Chemistry, Tokyo Institute of Technology, O-okayama,Meguro-ku, Tokyo, Japan

MASAAKI SUZUKI, Department of Biomolecular Science, Faculty of Engineering, GifuUniversity, Yanagido, Gifu, 501-1193, Japan

JAMESM TAKACS, Department of Chemistry-841 HAH, University of Nebraska-Lincoln,Lincoln, Nebraska, 68588-0304, USA

KENTARO TAKAGI, Department of Chemistry, Faculty of Science, Okayama University,Tsushima-naka, Okayama, 700-8530, Japan

TAKASHI TAKAHASHI, Department of Applied Chemistry, Graduate School of Scienceand Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro, Tokyo,152-8552, Japan

TAMOTSUTAKAHASHI, Catalysis Research Center, Hokkaido University, Sapporo, 060,Japan

YOSHINAO TAMARU, Department of Applied Chemistry, Faculty of Engineering,Nagasaki University, 1-14 Bunkyo, Nagasaki, 852-8521, Japan

ZE TAN, Herbert C Brown Laboratories of Chemistry, Purdue University, WestLafayette, Indiana, 47907-1393, USA.

SERGETHORIMBERT, Universite Pierre et Marie Curie (Paris VI), Laboratoire de Chimie ganique de Synthese, Case 229, T 44 2éme ET., 04 Place Jussieu, 75252 Paris, Cedex 05,France

Or-JIRO TSUJI, Professor Emeritus of Tokyo Institute of Technology, Tsu 602-128Kamakura, 248-0032, Japan

YASUSHI TSUJI, Catalysis Research Center, Hokkaido University, Sapporo, 060-0811,Japan

SHIN-ICHIRO UCHIUMI, Corporate Research and Development, UBE Industries, Ltd.,1978-5 Kogushi, Ube, Yamaguchi, 755-8633, Japan

KJELL UNDHEIM, Department of Chemistry, University of Oslo, Blindern, 0315 Oslo,Norway

JONATHAN M J WILLIAMS, School of Chemistry, University of Bath, Bath, BA2 7AY,United Kingdom

CAIDING XU, Affymax Research Institute, 4001 Miranda Ave Palo Alto, California

KRISTERZETTERBERG, School of Chemistry and Chemical Engineering, Royal Institute

of Technology, Teknikringen 56, S-100 44 Stockholm, Sweden

TONY Y ZHANG, Lilly Research Laboratories DC 4813, Lilly Corporate Center,Indianapolis, Indiana 46285, USA

xxxii CONTRIBUTORS

Cp, CyclopentadienylCSA, Camphosulfonic acid

Cy, CyclohexylDABCO, 1,4-Diazobicyclo[2.2.2]octaneDBA(often shown as dba), Dibenzalace-tone

DBN, 1,5-Diazabicyclo[4.3.0] non-5-ene

DBPF, 1–Bis–di–t–butylphosphinoferrocene

DBU, 1,8-Diazabicyclo[5.4.0] undec-7-eneDCC, 1,3-DicyclohexylcarbodiimideDCD model, Dewar–Chatt–Duncansonmodel

DCE, DichloroethaneDDQ, 2,3-Dichloro-5,6-dicyano-1, 4-benzoquinone

DEA, DiethylamineDEAD, DiethylazodicarboxylateDec, Decyl

DFT, Density functional theoryDIBAH, Diisobutylaluminum hydrideDIBAL-H DIBAH (sometimes shown asDIBAL)

DIEA, Diisopropylethylamine

DIOP, (4R,5R)–trans–4,5–

Bis[(diphenylphosphino)methyl]–2;2–dimethyl–1,3–dioxolane,Diphos, See DPE

DMA, N,N–Dimethylacetamide

DMAD, Dimethyl acetylenedicarboxylateDMAP, 4-DimethylaminopyridineDME, Dimethoxyethane

DMF, DimethylformamideDMI, 1,3–Dimethyl–2–imidazolidinone,N,N–Dimethyl–2–imidazolidinone

EWG, Electron–withdrawing group

FBS, Fluorous biphasic system

FOS, Formal oxidation state

GPC, Gel permeation chromatography

ICPs, Integrated chemical processes

i-, Iso- i-Pr or iPr, Isopropyl

L, Ligand

LAH, Lithium aluminum hydride, LiAlH4

LDA, Lithium diisopropylamide

LED, Light–emitting diodes

LUMO, Lowest unoccupied molecular

NIS, N-Iodosuccinimide

NIT, Nitronyl nitroxide

NMM, N–methylmorpholine NMP, N–Methylpyrrolidone

NMR, Nuclear magnetic resonanceNOE, Nuclear Overhauser effect

NORPHOS, Bis(diphenylphosphino)bicyclo[2.2.1]hept-5-ene

2,3-Oct, OctylPAA, PolyacrylamidePCC, Pyridinium chlorochromatePDC, Pyridinium dichromatePEG, Polyethylene glycolPent, Pentyl

PFS, Pentafluorostyrene

PG, Prostaglandin

Ph, PhenylPHANEPHOS, 4,12-Bis(diphenylphos-phino)[2.2]paracyclophane

Phen, 1, 10-PhenanthrolinePHOPHOS,

2,2–Bis(diphenylarsino)–1,1binaphthyl

PL, PhotoluminescencePMHS, PolymethylhydrosiloxanePMP, 1, 2, 6–PentamethylpiperidinePPA, Polyphosphoric acid

PPE, Poly(phenylene ethinylene)

PPP, Poly(para-phenylene)

Pr, n-Propyl

Py, PyridinePROPHOS, 1,2-Bis(diphenylphosphino)propanePTA, 1,3,5–Triaza–7–phosphaadamantanePTC, Phase–transfer catalyst

PTSA, p-Toluenesulfonic acid

R, An organic groupRAMP, R-()-Amino-2-(methoxymethyl)pyrrolidine

Rf, PerfluoroalkylRed-Al, Na[AlH2(MeOCH2CH2O)2]SAMP, S-()-Amino-2-

(methoxymethyl)pyrrolidine

Sec; s, Secondary s-Bu, s Bu, sec-Bu, Secondary butyl.

TMM-Pd, Trimethylenemethane palladiumTMOF, Trimethyl orthoformate

PART V

Palladium-Catalyzed Reactions Involving Nucleophilic Attack on Ligands

Handbook of Organopalladium Chemistry for Organic Synthesis, Edited by Ei-ichi Negishi

ISBN 0-471-31506-0 © 2002 John Wiley & Sons, Inc.

V.1 Background for Part V

EI-ICHI NEGISHI

As discussed in Part I, complexation with transition metals renders -compounds morereactive toward nucleophilic reagents Thus, ,-unsaturated organopalladiums, such asallyl- and propargylpalladium derivatives, readily react with a wide variety of nucle-ophilic reagents to undergo nucleophilic substitution reactions in which Pd serves as the

key atom in a leaving group (Sect V.2) The attacking reagents may be carbon ophiles (Sect V.2.1), group 16 and 15 atom nucleophiles (Sect V.2.2), as well as hydro- gen and metal nucleophiles (Sect V.2.3).

nucle-The reaction of butadiene with PdCl2reported in 1957[1]most probably represents thefirst synthesis of allylpalladium complexes This was followed by the development of their preparation via oxidative addition of allylic electrophiles[2]and transmetallation[3]as

discussed in Sect II.3 Early investigations of allylpalladiums, however, mainly dealt with

structural and other organometallic aspects

From the organic synthetic viewpoint, the report in 1965 by Tsuji et al [4]on the tion of -allylpalladium chloride with diethyl sodiomalonate to give the allylated

reac-malonate (Scheme 1) was a significant milestone, marking the birth of the Tsuji–Trost

reaction Interestingly, however, this reaction remained stoichiometric in Pd for severalyears, and its catalytic versions were developed only in the 1970s.[5 ]–[9] Over the lastquarter of the century, the chemistry of allylpalladium and related derivatives, especiallytheir substitution reactions, has become one of the most important branches of organopal-ladium chemistry from the viewpoint of organic synthesis

Oxidative addition of Pd to ,-unsaturated alkyl electrophiles has been shown toproceed with inversion.[10]This process is generally thought to involve prior -complex-ation followed by intramolecular nucleophilic displacement of a leaving group by Pd

with inversion (Sect II.3) Depending on ligands, solvents, and other structural

parame-ters, either - or -complexes may be formed, even though distinction between them isoften very loosely made In fact, their representation using -allyl structures has beenwidely practiced Although this practice is probably correct and reasonable in mostcases, casual selection of the -allylpalladium structures may have to be questioned insome cases

Depending primarily on the nature of nucleophiles, either attack on the -allylligand or attack at Pd has been observed Thus, for example, the reaction of -

allylpalladium complexes with soft carbon nucleophiles generally involves attack on

the -allyl ligands proceeding via inversion at the site of substitution leading to

Handbook of Organopalladium Chemistry for Organic Synthesis, Edited by Ei-ichi Negishi

ISBN 0-471-31506-0 © 2002 John Wiley & Sons, Inc.

1664 V Pd-CATALYZED REACTIONS INVOLVING NUCLEOPHILIC ATTACK ON LIGANDS

substitution, of allylic electrophiles with overall retention,[11] whereas their reaction

with hard carbon nucleophiles, such as organometals containing Mg, Zn, Al, and so

on, must involve attack at Pd, which is followed by reductive elimination to effect anallylic substitution with overall inversion at the allylic carbon atom.[12] For this andother reasons, the Pd-catalyzed cross-coupling reactions of allylic derivatives with

hard organometals are discussed in Part III (Sects III.2.9 and III.2.10)

Hydrogenol-ysis of ,-unsaturated alkyl derivatives via Pd-catalyzed nucleophilic substitutionalso proceeds with an overall inversion, suggesting that H nucleophiles attack Pdrather than -ligands For practical reasons, however, it is discussed in this Part (Sect V.2.3.1) rather than in Sect III.3.1 Hydrogenolysis not only provides a means of re-

ducing ,-unsaturated organic electrophiles but also serves as a method of removal ofsuch unsaturated groups from their derivatives containing alcohols, carboxylic acids,amines, and other active hydrogen-containing compounds, thereby providing a method

for their deprotection (Sect V.2.3.2).

The Pd-catalyzed reactions of allylic electrophiles with metal nucleophiles can

pro-duce the corresponding allylmetal derivatives (Sect V.2.3.3), which can, in turn, serve as

allylic nucleophiles This protocol provides a means of utilizing allylpalladium and

related derivatives as nucleophiles rather than electrophiles (Sect V.2.3.4) Many of the

substitution reactions mentioned above can be asymmetric Because of their special nificance in organic synthesis, Pd-catalyzed asymmetric allylation and related reactions

sig-are discussed in Sect V.2.4.

Although the chemistry of allylpalladium and related derivatives has been dominated

by substitution reactions, they also undergo other types of reactions, such as addition,elimination, and rearrangement Elimination of allylpalladium derivatives gives conju-

gated dienes, as discussed in Sect V.2.5.1 While this may constitute an undesirable side

reaction in the substitution reactions, it can also provide an attractive route to conjugateddienes -Trialkylsilymethyl-substituted allypalladium derivatives have been shown toserve as dipolar trimethylenemethane derivatives and participate in [3 2], [3  4], and

other cycloaddition reactions These reactions are discussed in Sect V.2.5.2 The

am-bident nature of allyl, propargyl, and allenyl derivatives leads to [1,3] rearrangements,which can be catalyzed by Pd In cases where the anionic moiety is also ambident, as isoften the case, Pd-catalyzed [3,3] rearrangements may be observed These rearrange-

ments are discussed in Sect V.2.5.3 Another topic of growing significance in this area is

the synthesis of natural products via allylpalladium and related derivatives discussed in

Sect V.2.6.

Mainly for practical reasons, other topics are discussed in other parts In addition toPd-catalyzed cross-coupling involving allyl, propargyl, and allenyl derivatives discussed

in Sects III.2.9 and III.2.10, allylpalladation and related reactions with alkenes, alkynes,

and other -compounds, which can best be viewed as carabopalladation processes, are

discussed in Sect IV.4, while carbonylation and related reactions of allylpalladium and related derivatives are discussed in Sect VI.3.

-Complexation of Pd with alkenes, alkynes, and related -compounds also leads totheir activation toward nucleophiles In contrast with the formation of allyl-, propargyl-,and allenylpalladium derivatives, however, no oxidative addition is involved in the cases

of alkenes and alkynes This difference is responsible for the contrasting behavior exhibited by these two classes of compounds toward nucleophiles, as summarized in

elec-it possible to devise catalytic processes welec-ithout any external reagents, as amply

demon-strated in Sect V.2 On the other hand, the same nucleophiles undergo formal addition

with P d – alkene -complexes to produce 1 Neither oxidation nor reduction occurs in

this reaction As such, this reaction is only stoichiometric in Pd, and it must therefore befollowed by one or more additional processes in which Pd is dissociated from organicproducts for both completion of organic synthesis and recycling Pd complexes as cata-lysts One such process is -dehydropalladation, which is thought to be a key step in theWacker oxidation[13],[14](Sect V.3.1.1) and related reactions (Sect V.3.1.2) This process

does complete an organic synthesis, but Pd complexes are reduced to Pd(0) species As aresult, reoxidation of Pd(0) species to Pd(II) species is necessary to complete a cycle that

is catalytic in Pd A wide variety of external oxidants including O2used in conjunctionwith CuCl2 have been employed to effect oxidation of Pd(0) species back to Pd(II)species

One very significant finding that appears to have gradually evolved in this area is that

-dehydropalladation can be substituted with reductive elimination reactions as shown in

Scheme 3 In cases where the reductive elimination step is followed by oxidative addition

of organic halides, active hydrogen compounds, and others used as the starting pounds, the overall process can be catalytic in Pd Indeed, a number of synthetically at-tractive Pd-catalyzed tandem and cascade processes of this class have been developed, as

com-discussed in Sects V.3.1.3, V.3.2.2, V.3.3.2, and V.3.4.

As in the allylic substitution reactions, a wide variety of nucleophiles including

oxy-gen and other group 16 atom nucleophiles (Sects V.3.1 and V.3.2), nitrooxy-gen and other group 15 atom nucleophiles (Sect V.3.3), and carbon nucleophiles (Sect V.3.4) have

been employed for nucleophilic attack on the ligands of Pd–alkene and Pd–alkyne complexes In cases where an organic halide is used as one of the starting compounds, the

-1666 V Pd-CATALYZED REACTIONS INVOLVING NUCLEOPHILIC ATTACK ON LIGANDS

overall process may appear to proceed via carbopalladation as shown in the top half of

-alkenyl-palladium species is generally not a facile process Furthermore, the observed chemical outcome is not consistent with the carbopalladation–substitution tandem Onthe other hand, a tandem process consisting of nucleophilic attack on the -ligand of a

stereo-Pd – alkyne -complex and reductive elimination is in agreement with the observed

re-sults (Sect V.3.4) A similar dichotomy of syn- versus anti-addition has also been

ob-served in halopalladation (Sect V.3.5).

R

R Nu

R

X −

Nu R

-complexation with chiral Pd complexes can, in principle, lead to asymmetric processes

A number of natural products have been synthesized using various reactions discussed

in Sect V.3, as indicated by the examples shown in Sect V.3.6 Despite a fair number of examples discussed in Sect V.3.6, this area of research still remains relatively unex-

plored Thus, for example, natural products synthesis via Pd-catalyzed lactonization of alkynoic acids had not been reported until a few years ago.[ 1 7 ]–[19] Undoubtedly, manymore examples will be published in the future

Engl., 1962, 1, 80.

V.2 Palladium-Catalyzed

Nucleophilic Substitution Involving

Allylpalladium, Propargylpalladium,

and Related Derivatives

Carbon–Carbon Bond Formation Reactions

Carbon–Corbon Bond Formation via

-Allylpalladium and Propargylpalladium

is the first example of the carbon–carbon bond formation mediated by a Pd complex

(Scheme 1).[1] In addition to the allylation of malonate, the reaction of cyclohexanoneenamine with -allylpalladium chloride gave 2-allylcyclohexanone after hydrolysis.[1]Thediscovery of the allylation of nucleohphiles with -allylpalladium chloride means the birth

of -allylpalladium chemistry, which has developed as a remarkably useful syntheticmethod

Handbook of Organopalladium Chemistry for Organic Synthesis, Edited by Ei-ichi Negishi

ISBN 0-471-31506-0 © 2002 John Wiley & Sons, Inc.

R

X + NuH