Handbook of organopalladium chemistry for organic synthesis vol 1 negishi

HANDBOOK OFORGANOPALLADIUM CHEMISTRY FOR ORGANIC SYNTHESIS Volume 1 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 1

HANDBOOK OF

ORGANOPALLADIUM CHEMISTRY FOR ORGANIC SYNTHESIS

Volume 1

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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I.1 Historical Background of Organopalladium Chemistry 3

Ei-ichi Negishi

I.2 Fundamental Properties of Palladium and Patterns of the

Ei-ichi Negishi

IN SITU GENERATION, AND SOME PHYSICAL AND CHEMICAL

PROPERTIES

Ei-ichi Negishi

II.2 Pd(0) and Pd(II) Compounds without Carbon–Palladium Bonds 41

Ei-ichi Negishi

Ei-ichi Negishi

Dani¯ele Choueiry and Ei-ichi Negishi

Kunio Hiroi

King Kuok (Mimi)Hii

v

II.2.6 Palladium Complexes Containing Metal Ligands 91

Koichiro Oshima

Masamichi Ogasawara and Tamio Hayashi

II.3 Organopalladium Compounds Containing Pd(0) and Pd(II) 127

Ei-ichi Negishi

III.2 Palladium-Catalyzed Carbon–Carbon Cross-Coupling 229

Ei-ichi Negishi

Akira Suzuki

Masanori Kosugi and Keigo Fugami

Tamejiro Hiyama and Eiji Shirakawa

Luigi Anastasia and Ei-ichi Negishi

Shouquan Huo and Ei-ichi Negishi

Kjell Undheim

III.2.8 Palladium-Catalyzed Alkynylation 493

Kenkichi Sonogashira

Ei-ichi Negishi and Carding Xu

Ei-ichi Negishi and Fang Liu

Benzyl-, or Propargylmetals and Allyl, Benzyl,

Ei-ichi Negishi and Baiqiao Liao

Ei-ichi Negishi and Sebastien Gagneur

Homopropargyl-, or Homobenzylmetals

Ei-ichi Negishi and Fanxing Zeng

Takumichi Sugihara

Takumichi Sugihara

III.2.14.1 Palladium-Catalyzed -Substitution Reactions

of Enolates and Related Derivatives Other

Ei-ichi Negishi

Ei-ichi Negishi and Asaf Alimardanov

Ei-ichi Negishi and Yves Dumond

Tamio Hayashi

Bruce H Lipshutz

A Dieter Schlüter and Zhishan Bo

Ze Tan and Ei-ichi Negishi

Christian Amatore and Anny Jutand

Martin Kotora and Tamotsu Takahashi

III.3 Palladium-Catalyzed Carbon–Hydrogen and Carbon–

Anthony O King and Robert D Larsen

John F Hartwig

John F Hartwig

Akira Hosomi and Katsukiyo Miura

IV PALLADIUM-CATALYZED REACTIONS INVOLVING

CARBOPALLADATION

Stefan Bräse and Armin de Meijere

IV.2 The Heck Reaction (Alkene Substitution via Carbopalladation–

Dehydropalladation) and Related Carbopalladation Reactions 1133

Mats Larhed and Anders Hallberg

Stefan Bräse and Armin de Meijere

Matthias Beller and Alexander Zapf

Stefan Bräse and Armin de Meijere

Gerald Dyker

Masakatsu Shibasaki and Futoshi Miyazaki

Sergei I Kozhushkov and Armin de Meijere

Sandro Cacchi and Giancarlo Fabrizi

Vladimir Gevorgyan and Yoshinori Yamamoto

IV.3 Palladium-Catalyzed Tandem and Cascade Carbopalladation

Termination with Alkenes, Arenes, and

Stefan Bräse and Armin de Meijere

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

IV.4 Allylpalladation and Related Reactions of Alkenes, Alkynes,

Takashi Takahashi and Takayuki Doi

IV.5 Alkynyl Substitution via Alkynylpalladation–Reductive

Vladimir Gevorgyan

Keisuke Suzuki and Ken Ohmori

and Removal of Carbon Tethers via Carbopalladation

IV.9 Cyclopropanation and Other Reactions of

Oliver Reiser

IV.10 Carbopalladation via Palladacyclopropanes

James M Takacs

Shinichi Saito and Yoshinori Yamamoto

Armin de Meijere and Oliver Reiser

Paul Knochel

VOLUME 2

NUCLEOPHILIC ATTACK ON LIGANDS

Ei-ichi Negishi

V.2 Palladium-Catalyzed Nucleophilic Substitution Involving

Allylpalladium, Propargylpalladium, and Related Derivatives 1669

Jiro Tsuji

Allylic Halides, Carboxylates, Ethers, and Related

Lara Acemoglu and Jonathan M J Williams

Marcial Moreno-Mañas and Roser Pleixats

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

Ei-ichi Negishi and Show-Yee Liou

Christine Courillon, Serge Thorimbert, and Max Malacrìa

Sulfur and Other Heavier Group 16

Kunio Hiroi

of Nitrogen and Other Group 15 Atom-Containing

Shun-Ichi Murahashi and Yasushi Imada

Tadakatsu Mandai

V.2.1.9 Palladium-Catalyzed Reactions

of Soft Carbon Nucleophiles with Dienes,

Hiroyuki Nakamura and Yoshinori Yamamoto

Substitution with Nitrogen, Oxygen, and Other Groups

of Allylic, Propargylic, and Related Electrophiles

Tadakatsu Mandai

Conjugated Dienes and Allylpalladium

Pher G Andersson and Jan-E Bäckvall

Derivatives in Allylic Substitution with O, N

Björn Åkermark and Krister Zetterberg

Katsuhiko Inomata and Hideki Kinoshita

Mark Lipton

Yasushi Tsuji

Yoshinao Tamaru

Lara Acemoglu and Jonathan M J Williams

Isao Shimizu

Sensuke Ogoshi

V.2.5.3 Rearrangements of Allylpalladium

Pavel Kocˇovsk´y and Ivo Star´y

Véronique Michelet, Jean-Pierre Genêt, and Monique Savignac

V.3 Palladium-Catalyzed Reactions Involving Nucleophilic

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

Patrick M Henry

Takahiro Hosokawa and Shun-Ichi Murahashi

Takahiro Hosokawa and Shun-Ichi Murahashi

Takahiro Hosokawa and Shun-Ichi Murahashi

Domino Reactions with Organopalladium

Sandro Cacchi and Antonio Arcadi

Takahiro Hosokawa

Sandro Cacchi and Fabio Marinelli

Palladium–Alkene, Palladium–Alkyne, and Related

Geneviève Balme, Didier Bouyssi, and Nuno Monteiro

V.3.5 Palladium-Catalyzed Reactions via Halopalladation

Xiyan Lu

Caiding Xu and Ei-ichi Negishi

RELATED REACTIONS INVOLVING MIGRATORY INSERTION

Ei-ichi Negishi

VI.2 Migratory Insertion Reactions of Alkyl-, Aryl-, Alkenyl-,

and Alkynylpalladium Derivatives Involving Carbon Monoxide

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

Miwako Mori

Hydrocarbo-xylation and Related Carbonylation

Bassam El Ali and Howard Alper

via Palladium-Catalyzed Carbonylative

Vittorio Farina and Magnus Eriksson

by Carbonylative Esterification, Amidation,

Hans-Günther Schmalz and Oliver Geis

Yong-Shou Lin and Akio Yamamoto

Yoshinao Tamaru and Masanari Kimura

VI.2.3 Reactions of Acylpalladium Derivatives with Enolates

Ei-ichi Negishi and Hidefumi Makabe

Robert D Larsen and Anthony O King

VI.3 Migratory Insertion Reactions of Allyl, Propargyl,

and Allenylpalladium Derivatives Involving Carbon Monoxide

Tadakatsu Mandai

VI.4 Acylpalladation and Related Addition Reactions 2519

Alkenes, Alkynes, and Related Unsaturated Compounds 2519

Christophe Copéret and Ei-ichi Negishi

Youichi Ishii and Masanobu Hidai

Giambattista Consiglio

Christophe Copéret

Gian Paolo Chiusoli and Mirco Costa

Bartolo Gabriele and Giuseppe Salerno

Jiro Tsuji

Hiroshi Okumoto

VI.6 Synthesis of Natural Products via

Miwako Mori

VI.7 Palladium-Catalyzed Carbonylative Oxidation 2683

Yuzo Fujiwara and Chengguo Jia

Shin-ichiro Uchiumi and Kikuo Ataka

VI.8 Synthesis of Oligomeric and Polymeric Materials via

Palladium-Catalyzed Successive Migratory Insertion of Isonitriles 2705

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

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

Hydrogenation with Dihydrogen and

Ariel Haskel and Ehud Keinan

VII.3 Palladium-Catalyzed Isomerization of Alkenes, Alkynes,

and Related Compounds without Skeletal Rearrangements 2783

Ei-ichi Negishi

Hidefumi Makabe and Ei-ichi Negishi

VII.5 Metallopalladation 2825

Koichiro Oshima

VII.6 Palladium-Catalyzed Syn-Addition Reactions of

X—Pd Bonds (X  Group 15, 16, and 17 Elements) 2841

Akiya Ogawa

HAVE NOT BEEN DISCUSSED IN EARLIER PARTS

Ei-ichi Negishi

VIII.2 Oxidation via Reductive Elimination of Pd(II)

Yuzo Fujiwara and Chengguo Jia

Yuzo Fujiwara

VIII.3 Palladium-Catalyzed or -Promoted Oxidation

Yoshihiko Ito and Michinori Suginome

Shun-Ichi Murahashi and Naruyoshi Komiya

Yuzo Fujiwara and Ei-ichi Negishi

VIII.4 Other Miscellaneous Palladium-Catalyzed or -Promoted

Ei-ichi Negishi

REACTIONS CATALYZED BY PALLADIUM

Ei-ichi Negishi

IX.2 Rearrangement Reactions Catalyzed by Palladium 2919

Hiroyuki Nakamura and Yoshinori Yamamoto

Ei-ichi Negishi

Masaaki Suzuki, Takamitsu Hosoya, and Ryoji Noyori

CHEMISTRY

Irina P Beletskaya and Andrei V Cheprakov

X.2 Palladium Catalysts Immobilized on Polymeric Supports 3007

Tony Y Zhang

X.3 Organopalladium Reactions in Combinatorial Chemistry 3031

Stefan Bräse, Johannes Köbberling, and Nils Griebenow

R.1 General Guidelines on References Pertaining to Palladium

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-xix

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.

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,

two-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

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University, S-106 91 Stockholm, Sweden

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8304 Minamiminowa Kamiina, Nagano, 399-4598, Japan

Organique de Synthèse, 75252 Paris, Cedex 05, France

Science and the Arts, 2640 Nishinoura, Tsurajima, Kurashiki, 712-8505, Japan

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

Synthèse Sélective Organique et Produits Naturels, UMR C.N.R.S 7573, 11, ruePierre et Marie Curie, 75231 Paris, Cedex 05, France

Sciences, University of Tsukuba, Tsukuba, Ibaraki, 305-8571, Japan

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

1, 69622, Villeurbanne Cédex, France

Barcelona, Edifici C, 08193 Cerdanyola (Barcelona), Spain

Sapporo, 060-0812, Japan

Science, Ridai-cho 1-1 Okayama, 700-0005, Japan

University, Sendai, 980-8578, Japan

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

Chikusa, Nagoya, 464, Japan

University, Sakyo, Kyoto, 606-8502, Japan

Univer-sity, Kitauoyanishi-machi, Nara, 630-8506, Japan

University, Suita, Osaka, 565-0871, Japan

O-okayama, Meguro-ku, Tokyo, 152-8551, Japan

Science 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

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

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

Science and Technology, Asahidai, Tatsunokuchi, Ishikawa, 923-1292, Japan

Engineering, Fukui University of Technology, 3-6-1, Gakuen, Fukui, 910-8505,Japan

the Czech Republic, Flemingovo 2, 16610 Prague 6, Czech Republic

Univer-sity, Yamashiro-cho Tokushima, 770-8514, Japan

Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto, 606-8501, Japan

and the Arts, Kurashiki, 712-8505, Japan

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

University, Yanagido, Gifu, 501-1193, Japan

Lincoln, Nebraska, 68588-0304, USA

Tsushima-naka, Okayama, 700-8530, Japan

and Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro, Tokyo,152-8552, Japan

Japan

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

Kamakura, 248-0032, Japan

Japan

1978-5 Kogushi, Ube, Yamaguchi, 755-8633, Japan

University, 3-4-1 Ohkubo, Shinjuku, Tokyo, 169-8555, Japan

University, Sendai, 980-8578, Japan

ALEXANDERZAPF, Institut für Organische Katalyseforschung an der Universität RostockE.V (IfOK), Buchbinderstr 5-6, D-18055 Rostock, Germany

Lafayette, Indiana, 47907-1393, USA

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

Indianapolis, Indiana 46285, USA

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 hydride

DIBAL)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,

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

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,

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

TMM-Pd, Trimethylenemethane palladiumTMOF, Trimethyl orthoformate

PART I

Introduction and Background

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

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

I.1 Historical Background of

Organopalladium Chemistry

EI-ICHI NEGISHI

This Handbook is all about the use of palladium (Pd) mostly as a component of catalystsfor organic synthesis Today, it is widely recognized that Pd has very significantlychanged and improved the art of organic synthesis over the last three decades It seemsreasonable to state that Pd already is one of the most versatile, useful, and hence signifi-cant metals in organic synthesis along with Li, Mg, B, Cu and a few others and that itssignificance is still sharply rising Over 1000 research publications dealt with the use of

Pd mostly in organic synthesis in 1998 alone

One question this author has frequently encountered is: Why is Pd so versatile anduseful? This is indeed a good question, which is not so easy to answer, but some attempts

will be made later in Sect I.2 In this section, however, let us look back and try to

become acquainted with some of the notable events in the history of organopalladiumchemistry with emphasis on the use of Pd in organic synthesis

In 1912 V Grignard and P Sabatier shared, for the first time, a Nobel Prize in

main group organometallic chemistry and Sabatier’s catalytic transition metal chemistrywere correctly recognized in a largely prophetic manner by the Royal Swedish Academy

of Sciences almost a century ago It is also striking that the developments of both areas up

to that point were rather slow, circuitous, and evolutionary in many ways The discoveryand development of Grignard reagents spanned roughly half a century after Frankland’s

syn-thetic utility of the Grignard reagents have only increased with time Along with

of organometallic compounds

The development of organopalladium chemistry for organic synthesis has been evenmore sluggish than that of the organometallic chemistry of Mg and Li It has been

after the asteroid Pallas, which was discovered a year before Although an ethylene

3

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

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

complex of Pt, commonly known as Zeise’s salt, was reported as early as 1827,[7] littlewas known a bout either organopalladiums or the use of Pd in organic synthesis during

a century ago was instrumental in laying the foundation for the widespread use of alytic hydrogenation in both academia and industry However, he clearly stated in his

Nobel Lecture is an accurate indication, he used mostly Ni along with Pt, Co, Cu, and Ag

cat-alytic reduction including that of alkenes and alkynes had been reported by various

clearly established later, organopalladiums serve as intermediates in these reactions Inthis Handbook, catalytic hydrogenation and related addition reactions are discussed

mainly in Part VII, with other related reactions being discussed in several other sections including II.2.1, II.2.5, III.3.1, and VI.2.4 As important as these earlier developments of

Pd-catalyzed hydrogenation and related reduction reactions were in the area of organicsynthesis, they nevertheless represented an isolated, largely technological, and practicaldiscipline and had remained so until recently

made Pd an important transition metal for organic synthesis, even though Pd may haveshown some catalytic activities in these investigations

repre-sent one of the most important milestones in the history of organopalladium chemistry.Although not widely known, the stoichiometric conversion of ethylene to acetaldehyde

intricacy, however, the catalytic hydrogenation and the Wacker oxidation firmly established that Pd and its compounds can serve as catalysts for both reduction andoxidation At its core, the Wacker process involves a stoichiometric oxypalladation –

dehydropalladation tandem (Scheme 1), and the development of a catalytic process

(Scheme 2), as detailed in Sect V.3 More recent results have clearly indicated that

the scope of the Wacker oxidation can be and has indeed been expanded far beyondthe initial oxidation of ethylene and 1-alkenes to give aldehydes and ketones Thus,related aminopalladation, halopalladation, and other addition reactions of heteroatom-

Pd bonds have been developed Furthermore, these addition reactions can provideorganopalladium intermediates that can be used further for the formation of additional

bonds including C — C bonds (Sect V.3).

In the meantime, many other types of oxidation reactions catalyzed by Pd have alsobeen discovered and developed These other Pd-catalyzed oxidation reactions are dis-

cussed in Part VIII For some practical reasons, however, a few additional oxidation actions involving C — C bond formation are discussed in earlier sections, such as Sects III.2.20, VI.4.4, and VI.7.

re-Mechanistic consideration of the Wacker reaction, which is thought to involve

reaction remained only stoichiometric in Pd for several years Once its catalytic

to as the Tsuji– Trost reaction, and it represents one of the most widely investigated areas

of the organopalladium chemistry (Scheme 4).

The birth of the Heck reaction, another important Pd-catalyzed C — C bond-forming

organometals containing Hg, Sn, and Pb with alkenes in the presence of one equivalent

of a Pd(II) complex leading to substitution of an alkenyl hydrogen with a carbon group of

the organometallic reagent, typically an organomercury (Scheme 5) Here again,

how-ever, history has been skewed by frequent and unfortunate omission of a closely related

bottom of Scheme 5 Unfortunately, both of these stoichiometric reactions were as such

not very attractive from the synthetic viewpoint It was not until three to four years later

as the Heck reaction, sometimes called the Mizoroki– Heck reaction (Scheme 5) As detailed in Part IV, this reaction has been shown to proceed via addition of C — Pd bond

to alkenes (i.e., carbopalladation), followed by dehydropalladation (Scheme 6) The use

of the term ‘‘Heck reaction’’ should be limited to those processes that involve thiscarbopalladation – dehydropalladation sequence, be they stoichiometric or catalytic It is

1 2

Scheme 2

Pd Cl

CHE 2

Pd Cl

CHE2

E E

Original stoichiometric version

Catalytic version of the Tsuji −Trost reaction

Scheme 6

important to do so because the scope of carbopalladation itself is considerably broader

than that of the Heck reaction, as can readily be seen in Part IV For example, Blomquist

alkynes proceeding via a series of carbopalladation, which do not fall within the tion of the Heck reaction

defini-The full synthetic scope and utility of those reactions that involve carbopalladationincluding the Heck reaction became apparent only in the 1980s through extensive

investigations by a number of workers, as detailed in Part IV The scope of

carbopal-ladation may conceptually be further expanded so as to include addition reactions ofpalladium–carbene complexes as well as palladacyclopropanes, palladacyclopropenes,

and higher palladacycles These reactions are also discussed in Part IV (i.e., Sects.

the birth of the transition metal-catalyzed carbonylation Initially, Co catalysts were mostextensively used, but the Rh-based processes have since been developed as a superiormethods Although Pd may have been tested along with several other metals, such as Fe,

Ru, and Ni, it has never been shown to be very useful in the hydroformylation reaction,

but clearly different reaction of alkenes with CO and alcohols in the presence of a Pd catalyst producing esters was one of the earliest, if not the earliest, reports describing a successful and potentially useful Pd-catalyzed carbonylation reaction This was soon followed by the discovery of another Pd-catalyzed carbonylation reaction of allylic

R

R COOR1

Scheme 7

By 1974 the latter reaction had been generalized, and a wide variety of organic halidesand other related electrophiles including alkenyl and aryl halides had been used, most no-

Pd-catalyzed carbonylation

Yet another important development in the area of Pd-catalyzed carbonylation is the velopment of acylpalladation and related carbonyl – Pd bond addition reactions Acylpal-ladation may be defined as a process of acyl – Pd bond addition to alkenes and alkynes.Clearly, it is a kind of carbopalladation reaction For practical reasons, however, it is dis-

de-cussed in Part VI together with other carbonylation reactions mentioned above Tsuji and

re-ported also in 1965 a Pd-catalyzed cyclic carbonylation of dienes with CO and methanol

(Scheme 9) Although the exact mechanism of the initiation is unclear, these reactions

must involve acylpalladation for crucial C — C bond formation As promising as theywere, they remained a couple of isolated studies until about 1980.

The potential for industrial use of the perfectly alternating alkene–CO copolymers

detailed in Sect VI.4.2 Independently and concurrently, a systematic investigation

-alkene-substituted organic halides This has led to the discovery and development of

Sects VI.4.1 and VI.4.3.

Cross-coupling between organometals and organic electrophiles, such as organichalides, is not only one of the most straightforward methods but also the potentially most

general method for the formation of carbon–carbon bonds (Scheme 10) Even so, the

de-velopment of cross-coupling in general and of the Pd-catalyzed version in particular hasbeen surprisingly sluggish In fact, Pd-catalyzed cross-coupling was one of the last to bedeveloped among the several fundamentally different patterns of C — C bond formation

that are widely observable with Pd, as discussed further in Sect I.2

+

CO (10 atm) cat PdLn

150 °C

COOMe O

with organolithiums and Grignard reagents Even their reactions with alkyl halides are

leading to the formation of homocoupled products, and so on, in addition to their petitive reactions with other electrophilic functional groups present in the reactants Although there were some exceptions, such as alkylation of alkynylmetals containing Liand Mg, direct cross-coupling was, in the main, something to be avoided and substitutedwith more reliable but more circuitous enolate-based methods Introduction and develop-

mentioned above Nonetheless, a number of other problems remained unsolved