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Titanium and Zirconium in Organic Synthesis. Edited by Ilan Marek Copyright c 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30428-2 (Hardback); 3-527-60067-1 (Electronic) Titanium and Zirconium in Organic Synthesis Edited by Ilan Marek Titanium and Zirconium in Organic Synthesis. Edited by Ilan Marek Copyright c 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30428-2 (Hardback); 3-527-60067-1 (Electronic) Further Reading from Wiley-VCH Ricci, A. (Ed.) Modern Amination Methods 2000. ISBN 3-527-29976-9 Krause, N. (Ed.) Modern Organocopper Chemistry 2001. ISBN 3-527-29773-1 Yamamoto, H. (Ed.) Lewis Acids in Organic Synthesis AComprehensive Handbook in Two Volumes 2000. ISBN 3-527-29579-8 Beller, M., Bolm, C. (Eds.) Transition Metals for Organic Synthesis Building Blocks and Fine Chemicals 1998. ISBN 3-527-29501-1 Titanium and Zirconium in Organic Synthesis. Edited by Ilan Marek Copyright c 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30428-2 (Hardback); 3-527-60067-1 (Electronic) Titanium and Zirconium in Organic Synthesis Edited by Ilan Marek Titanium and Zirconium in Organic Synthesis. Edited by Ilan Marek Copyright c 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30428-2 (Hardback); 3-527-60067-1 (Electronic) Editor: This book was carefully produced. Never- theless, editor, authors and publisher Prof. Ilan Marek do not warrant the information contained Department of Chemistry therein to be free of errors. Readers are Technion ± Israel Institute of Technology advised to keep in mind that statements, Haifa 32000 data, illustrations, procedural details or Israel other items may inadvertently be inaccurate. Library ofCongress Card No.: applied for A catalogue record for this book is available from the British Library. Die Deutsche Bibliothek ± CIP Cataloguing-in-Publication-Data A catalogue record for this publication is available from Die Deutsche Bibliothek. c WILEY-VCH Verlag GmbH, D-69469 Weinheim (Federal Republic of Germany), 2002 All rights reserved (including those of translation in other languages). No part of this book may be reproduced in any form ± by photoprintin microfil or any other means ± nor transmitted or translated into machine language without written permis- sion from the publishers. Registered names, trademarks, etc. used in this boo even when not specifically marked as suc are not to be considered unprotected by law. Printed in the Federal Republic of Germany. Printed on acid-free paper. Typesetting Hagedorn Kommunikatio Viernhei Germany Printing Strauss Offsetdruck Gmb MoÈrlenbach Bookbinding J. SchaÈffer GmbH & Co. K GruÈnstadt ISBN 3-527-30428-2 Titanium and Zirconium in Organic Synthesis. Edited by Ilan Marek Copyright c 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30428-2 (Hardback); 3-527-60067-1 (Electronic) V Foreword The time is apt for synthetic chemists to fully enter the world of organozirconium and organotitanium chemistry. While P Cu, and Ni catalyzed reactions have been embraced by synthetic practitioners and the long-standing hydrogenation catalysts, Rh and Ru, are being increasingly accepted for other uses, Zr and Ti reagents, wit of cours the notable exceptions of the polymerization catalysts, have not broken the barrier to widespread application for small molecule synthesis, espe- cially in industry. Aside from reagent availability and sensitivity, perhaps part of the explanation lies in the inability of the chemist trained in the Corey retrosyn- thetic analysis mold to adapt their thinking to what ar compared to more classical paths, the less rational dissection based on organozirconium and organotitanium reactions. This volum edited with dedication to content and care in presentation by Ilan Marek and encompassing forefront topics by the most active researchers in the field wil with reading and revisi provide persuasion to irreversibly change this perspective and to traverse the borders to new exciting synthetic chemistry. In a masterly introductory chapter, Negishi and Huo set the stage for zircono- cene chemistry, providing historical aspects which chronologically attribute the var- ious discoveries by numerous chemists in this fiel including the major contribu- tions from the Negishi laboratories and the systematic studies of hydrozirconation by Schwartz and his students, since the first report in 1954 of the structure of Cp2ZrCl2 by Wilkinson. In a innovative series of tabulated highlights, Negishi and Huo teach the generalizations and reactivity patterns of Zr(IV) and Zr(II), the most synthetically useful species, and provide X-ray structural and mechanistic insight wherever available. They also delineate what is currently feasible with Zr reagents (e. g. transmetallation) and where additional work may lead to new syn- thetic value (e. g. radical and photochemical reactions). The defined subsections (e. g. p-Complexatio Carbonylatio s-Bond Metathesis) allow the reader, both ex- pert and novic to quickly focus on given areas and easily pursue the relevant chapter for details. The discussion is concis mechanistically friendly to the syn- thetic organic chemis an whenever appropriat comparative (e.g effect of L M Z and Al in Zr-catalyzed cyclic carbometallation) thus providing a most use- ful overview of the topics in this volume. Takahashi and Li (Chapter 2) focus on the preparation and reactions of zircona- cyclopentadienes whic for a quarter of a century since their discovery in 1974 by VI Foreword Watt and Drummon were considered to be inert for C-C bond forming reactions. However, by the expedient of transmetallation to Cu, N Z L and A methodol- ogies for the stereoselective synthesis of olefins and dienes, as well as unusual het- erocycles, aromatics and their ring-annulated products are now available which are beginning to make impact on material scienc e. g. synthesis of pentacenes and polyphenylenes. Takahashi and Li provide evidence tha with further develop- ments in transmetallation and handling the zirconacycles outside of the Schlenk tube techniques, synthetic utility will increase and new catalytic reactions will be developed. In a fascinating chapter (Chapter 3) with considerable promise for synthetic chemists, Dixon and Whitby describe the insertion of carbenoids (a-halo-a-lithio species) into organozirconocenes. Setting the appropriate background of the me- chanistically analogous rapid insertion of the isoelectronic carbon monoxide and alkylisonitrile (which complements the Pauson-Khand reaction), the authors sys- tematically review the status of various halocarbenoids from which result synthetic methods for functionalized olefins, dienes, dienynes, among other organic mole- cules. The focus on the most extensively studied insertion of allyl carbenoids into zirconacycles leads to illustrations of tandem processes with initial demonstra- tion of application to natural product synthesis. Appropriate mechanistic specula- tion on very new processes suggests that this area offers a promising future for synthesis. Lipshutz, Pfeiffer, Noso and Tomioka (Chapter 4) assume the formidable task of providing a seven-year update of the advances in the hydrozirconation±transme- tallation sequence in organic synthesis. At the outse as expected from an experi- mental organic grou a discussion of practical aspects of the commercial CpZr(H)Cl (Schwartz reagent) are presented an similarly graciously, the difficul- ties of control of its reactions in appropriate air- and moisture-free atmosphere are stressed. Similarly expected is the emphasis on synthetic utility of the reactions, which involve acyl- and allylzirconocenes an most prominently, the cross-cou- pling reactions following transmetallation to Cu, Z B, and Ni. This survey invites the chemist to view anew various processes which were learned retrosynthetically by more traditional pathways, e. g. carbocyclizatio equivalency of acylzirconocenes as acyl anions and demonstrates in instructive schemes the impact that not only zirconium chemistry but other transition metal-catalyzed reactions have made on bioactive molecule and natural product synthesis. More specialized systems, e. g. vinyl tellurides, selenides, and phosphonates, are also effectively prepared. Recent reports (e. g. reduction of tertiary amide to aldehyde using the Schwartz reagent) and the promise of catalytic hydrozirconation will continue to fuel this area in the future. In useful and minor overlap with Chapters 3 and 4, the review (Chapter 5) on progress in acylzirconocene chemistry by Hanzawa points to the extensive mechan- istic investigation of this class of Zr reagents but lack of synthetic application. Following discussion of the stability and ease of handling of the RCOZr(Cl)Cp2 reagen its umpolung reactivity is delineated in general synthetic procedures for a-ketols, a-aminoketones (including Bronsted acid catalysis), selective 1,2-addition Foreword VII products of enones (including the first results of demonstration of enantioselectiv- ity). The closing sections on Pd- and Cu- catalyzed reactions of acylzirconocenes to give ketones appear to promise scope and the use of unsaturated acylzirconocenes as ketone a,b-dianion equivalents offer stimulus that the promise of this area may be imminent. With Chapter 6 by Hoveyda concerned with a critical review of chiral Zr catalysts in enantioselective synthesis, synthetic utility goes into high gear. A plethora of successful or highly promising asymmetric reactions (inter alia, inter- and intra- molecular alkylations, kinetic resolution of unsaturated exocyclic allylic ethers, hydrocyanatio
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