METHOD SUBCLASS PRODUCT Vol /3 C X bonds C X bonds. (Vols ) (Vols ) Synthesis. of Organic.

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2 rganizational Structure of Science of Synthesis* CATEGRY 1 rganometallics (Vols 1 8 ) 2 Hetarenes (Vols 9 17 ) Products of rganic Synthesis /3 C X bonds (Vols ) C X bonds (Vols ) C X bond (Vols ) 6 All C bonds (Vols 43 8 ) 4 Classification is based on the product, with all products belonging to one of six broad-ranging categories. All products occupy a strict hierarchical position in Science of Synthesis, defined according to the classification principles*. Products in Categories 3 6 are organized according to oxidation state, with products containing the greatest number of carbon heteroatom (C X) or C C -bonds to a single carbon occupying the highest positions (e.g., carboxylates, enolates, and alcoholates are covered in Categories 3, 4, and 5, respectively). * A complete description of the full classification principles can be found in the Science of Synthesis Guidebook. VLUME Vol. 9 PRDUCT CLASS Vol. 10 etc PRDUCT SUBCLASS METHD etc etc etc. VARIATIN etc. Selected Products and Reactions Each category is subdivided into volumes (see opposing page), each of which is devoted to discrete groupings of compounds called product classes (e.g., Thiophenes is Product Class 10 of Volume 9). Product classes may be further subdivided into, (e.g., Thiophene 1,1-Dioxides is Product product subclasses Subclass 3 of Product Class 10 of Volume 9). Consequently, the relationship between heading name and heading number varies below product class level within individual volumes. For each product class or subclass, a number of methods are described for synthesizing the general product type. ften there are variations on a method given. Both methods and variations contain experimental procedures with relevant background information and literature references. Selected display the scope and limitations of products and reactions the methods.

3 CATEGRY UPDATED VLUMES rganometallics a 8b (Vols 1 8 ) Hetarenes (Vols 9 17 ) 4/3 C X bonds a 20b (Vols ) 2 C X bonds a 31b (Vols ) 1 C X bond a 40b (Vols ) All C bonds a 45b 46 47a 47b 48 (Vols ) 2 Compounds of Groups 7 3 (Mn,Cr,V,Ti,Sc,La,Ac ) 4 Compounds of Group 15 (As, Sb, Bi) and Silicon Compounds 7 Compounds of Groups 13 and 2 (Al, Ga, In, Tl, Be Ba) 8a Compounds of Group 1 (Li Cs) 8b Compounds of Group 1 (Li Cs) 16 Six-Membered Hetarenes with Two Identical Heteroatoms 20a Three CarbonHeteroatom Bonds: Acid Halides; Carboxylic Acids and Acid Salts 21 Three CarbonHeteroatom Bonds: Amides and Derivatives; Peptides; Lactams 27 Heteroatom Analogues of Aldehydes and Ketones 40a Amines and Ammonium Salts * Detailed listings of product classes and subclasses, methods, and variations can be found in the Table of Contents sections of every volume.

4 Science of Synthesis Science of Synthesis is the authoritative and comprehensive reference work for the entire field of organic and organometallic synthesis. Science of Synthesis presents the important synthetic methods for all classes of compounds and includes: Methods critically evaluated by leading scientists Background information and detailed experimental procedures Schemes and tables which illustrate the reaction scope

5 Science of Synthesis Editorial Board E. M. Carreira C. P. Decicco A. Fuerstner G. A. Molander P. J. Reider E. Schaumann M. Shibasaki E. J. Thomas B. M. Trost Managing Director G. F. Herrmann Managing Editor Senior Scientific Editors Scientific Editors M. F. Shortt de Hernandez K. M. Muirhead-Hofmann M. H. Smith T. B. Reeve A. G. Russell M. Sainsbury M. J. White F. Wuggenig Georg Thieme Verlag KG Stuttgart New York

6 Science of Synthesis Knowledge Updates 2010/4 Volume Editors J. W. Bode (Vol. 21) E. M. Carreira (Vol. 20) K. Ishihara (Vol. 7) J. J. Li (Vol. 16) I. Marek (Vol. 2) M. estreich (Vol. 4) E. Schaumann (Vols. 27 and 40) M. Yus (Vol. 8) Responsible Members of the Editorial Board E. M. Carreira (Vol. 20) A. Fuerstner (Vol. 7) G. A. Molander (Vols. 16 and 21) E. Schaumann (Vols. 27 and 40) M. Shibasaki (Vols. 2 and 8) B. M. Trost (Vol. 4) Authors T. Aoyama T. Arai S. Araki J. L. Gleason Y. Hari T. Higashihara T. Hirashita G. Landelle P. Margaretha S. Matsunaga P. Merino H. Naka M. ishi J.-F. Paquin S. Saito T. Shioiri H. Takikawa E. A. Tiong M. Ueda M. Uemura M. Yamaguchi A. Yanagisawa J. Zhang 2011 Georg Thieme Verlag KG Stuttgart New York

7 IV 2011 Georg Thieme Verlag KG Rüdigerstrasse 14 D Stuttgart Printed in Germany Typesetting: process media consult Printing and Binding: AZ Druck und Datentechnik GmbH, Kempten Bibliographic Information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available on the internet at < Library of Congress Cataloging in Publication Data Science of synthesis : Houben Weyl methods of molecular transformations. p. cm. Includes bibliographical references and index. Contents: Science of Synthesis Knowledge Updates 2010/4 / volume editors, J. W. Bode, E. M. Carreira, K. Ishihara, J. J. Li, I. Marek, M. estreich, E. Schaumann, M. Yus ISBN rganic compounds Synthesis. I. Title: Houben Weyl methods of molecular transformations. QD262.S '.2 dc (Houben Weyl methods of organic chemistry) British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN Date of publication: March 23, 2011 Copyright and all related rights reserved, especially the right of copying and distribution, multiplication and reproduction, as well as of translation. No part of this publication may be reproduced by any process, whether by photostat or microfilm or any other procedure, without previous written consent by the publisher. This also includes the use of electronic media of data processing or reproduction of any kind. This reference work mentions numerous commercial and proprietary trade names, registered trademarks and the like (not necessarily marked as such), patents, production and manufacturing procedures, registered designs, and designations. The editors and publishers wish to point out very clearly that the present legal situation in respect of these names or designations or trademarks must be carefully examined before making any commercial use of the same. Industrially produced apparatus and equipment are included to a necessarily restricted extent only and any exclusion of products not mentioned in this reference work does not imply that any such selection of exclusion has been based on quality criteria or quality considerations. Warning! Read carefully the following: Although this reference work has been written by experts, the user must be advised that the handling of chemicals, microorganisms, and chemical apparatus carries potentially life-threatening risks. For example, serious dangers could occur through quantities being incorrectly given. The authors took the utmost care that the quantities and experimental details described herein reflected the current state of the art of science when the work was published. However, the authors, editors, and publishers take no responsibility as to the correctness of the content. Further, scientific knowledge is constantly changing. As new information becomes available, the user must consult it. Although the authors, publishers, and editors took great care in publishing this work, it is possible that typographical errors exist, including errors in the formulas given herein. Therefore, it is imperative that and the responsibility of every user to carefully check whether quantities, experimental details, or other information given herein are correct based on the users own understanding as a scientist. Scaleup of experimental procedures published in Science of Synthesis carries additional risks. In cases of doubt, the user is strongly advised to seek the opinion of an expert in the field, the publishers, the editors, or the authors. When using the information described herein, the user is ultimately responsible for his or her own actions, as well as the actions of subordinates and assistants, and the consequences arising therefrom.

8 V Preface As the pace and breadth of research intensifies, organic synthesis is playing an increasingly central role in the discovery process within all imaginable areas of science: from pharmaceuticals, agrochemicals, and materials science to areas of biology and physics, the most impactful investigations are becoming more and more molecular. As an enabling science, synthetic organic chemistry is uniquely poised to provide access to compounds with exciting and valuable new properties. rganic molecules of extreme complexity can, given expert knowledge, be prepared with exquisite efficiency and selectivity, allowing virtually any phenomenon to be probed at levels never before imagined. With ready access to materials of remarkable structural diversity, critical studies can be conducted that reveal the intimate workings of chemical, biological, or physical processes with stunning detail. The sheer variety of chemical structural space required for these investigations and the design elements necessary to assemble molecular targets of increasing intricacy place extraordinary demands on the individual synthetic methods used. They must be robust and provide reliably high yields on both small and large scales, have broad applicability, and exhibit high selectivity. Increasingly, synthetic approaches to organic molecules must take into account environmental sustainability. Thus, atom economy and the overall environmental impact of the transformations are taking on increased importance. The need to provide a dependable source of information on evaluated synthetic methods in organic chemistry embracing these characteristics was first acknowledged over 100 years ago, when the highly regarded reference source Houben Weyl Methoden der rganischen Chemie was first introduced. Recognizing the necessity to provide a modernized, comprehensive, and critical assessment of synthetic organic chemistry, in 2000 Thieme launched Science of Synthesis, Houben Weyl Methods of Molecular Transformations. This effort, assembled by almost 1000 leading experts from both industry and academia, provides a balanced and critical analysis of the entire literature from the early 1800s until the year of publication. The accompanying online version of Science of Synthesis provides text, structure, substructure, and reaction searching capabilities by a powerful, yet easy-to-use, intuitive interface. From 2010 onward, Science of Synthesis is being updated quarterly with high-quality content via Science of Synthesis Knowledge Updates. The goal of the Science of Synthesis Knowledge Updates is to provide a continuous review of the field of synthetic organic chemistry, with an eye toward evaluating and analyzing significant new developments in synthetic methods. A list of stringent criteria for inclusion of each synthetic transformation ensures that only the best and most reliable synthetic methods are incorporated. These efforts guarantee that Science of Synthesis will continue to be the most up-to-date electronic database available for the documentation of validated synthetic methods. Also from 2010, Science of Synthesis includes the Science of Synthesis Reference Library, comprising volumes covering special topics of organic chemistry in a modular fashion, with six main classifications: (1) Classical, (2) Advances, (3) Transformations, (4) Applications, (5) Structures, and (6) Techniques. Titles will include Stereoselective Synthesis, Water in rganic Synthesis, and Asymmetric rganocatalysis, among others. With expertevaluated content focusing on subjects of particular current interest, the Science of Synthesis Reference Library complements the Science of Synthesis Knowledge Updates, to make Science of Synthesis the complete information source for the modern synthetic chemist.

9 VI Preface The overarching goal of the Science of Synthesis Editorial Board is to make the suite of Science of Synthesis resources the first and foremost focal point for critically evaluated information on chemical transformations for those individuals involved in the design and construction of organic molecules. Throughout the years, the chemical community has benefited tremendously from the outstanding contribution of hundreds of highly dedicated expert authors who have devoted their energies and intellectual capital to these projects. We thank all of these individuals for the heroic efforts they have made throughout the entire publication process to make Science of Synthesis a reference work of the highest integrity and quality. The Editorial Board July 2010 E. M. Carreira (Zurich, Switzerland) E. Schaumann (Clausthal-Zellerfeld, Germany) C. P. Decicco (Princeton, USA) M. Shibasaki (Tokyo, Japan) A. Fuerstner (Muelheim, Germany) E. J. Thomas (Manchester, UK) G. A. Molander (iladelphia, USA) B. M. Trost (Stanford, USA) P. J. Reider (Princeton, USA)

10 VII Abstracts 2010 p Arene rganometallic Complexes of Chromium, Molybdenum, and Tungsten M. Uemura This review is an update to Section 2.4 and covers the literature from 1999 to (h 6 -Arene)chromium complexes have been considerably developed in organic synthesis on the basis of the strong electron-withdrawing ability and steric effect of the tricarbonylchromium fragment. The corresponding arenechromium complexes of unsymmetrical 1,2- or 1,3-disubstituted arene ligands are nonsuperimposable on their mirror images. Catalytic asymmetric synthesis of the planar chiral arenechromium complexes with chiral catalysts has been actively developed. The planar chiral arenetricarbonylchromium complexes have been widely employed in asymmetric synthesis, natural product synthesis, and increasingly as chiral ligands in asymmetric catalysis. This review focuses on the synthesis of planar chiral arenechromium complexes, and their applications in organic synthesis. (H) 2 B (C) 3 Cr CH Br 5 mol% Pd(P 3 ) 4 Na 2 C 3, MeH H 2, 75 o C 74% (C) 3 Cr CH (+) endo xylene, 140 o C, 2 h 70% 1. CH 2 () 2, MeH TsH, rt 2. Bu 2, 1,2-dichloroethane 140 o C, 2 h 3. 6 M HCl, THF, rt 44% (C) 3 Cr (C) 3 Cr CH exo CH ent-exo Keywords: asymmetric hydroboration asymmetric reduction of ketones atropisomer catalytic asymmetric synthesis chromium migration cross coupling cycloisomerization enantioselective lithiation gold catalysts higher-order cycloaddition nucleophilic substitution molecular switch axially chiral biaryl palladium catalyst planar chirality radical coupling 2010 Updated Section 2010 Completely Revised Contributions New New Contributions

11 VIII Science of Synthesis Abstracts 2010 p Diazo-1-silylalkanes Y. Hari, T. Aoyama, and T. Shioiri This manuscript is an update to Section describing methods for the synthesis and applications of 1-diazo-1-silylalkanes. This update focuses on papers published in the period Me 3 Si MgBr R 1 R 2 N 2 THF, 78 o C Me 3 Si H R 2 R 1 N 2 Keywords: silyldiazoalkanes diazo(trimethylsilyl)methane alkylidene carbenes Colvin rearrangement insertion reaction cyclopropanation [3+2] cycloaddition diazo(silyl)acetates diazo(silyl)methyl ketones 2010 p Aluminum Hydrides H. Naka and S. Saito This manuscript is an update to the earlier Science of Synthesis contribution describing methods for the preparation of aluminum hydrides used for organic synthesis, and recent advances in synthetic applications of aluminum hydrides. Various chemoselective reductions, such as partial reduction of esters, nitriles, or amides to aldehydes, are possible using aluminum hydrides with suitable ligands. Me N Na + Al Me H t-buk, toluene, t-bu <15 o C, 1 h 95% H BnN BnN Keywords: aluminum compounds chemoselectivity hydroalumination metal hydrides reduction reductive cyclization regioselectivity stereoselective synthesis 2010 Updated Section 2010 Completely Revised Contributions New New Contributions

12 Abstracts IX 2010 p Aluminum Halides H. Naka and S. Saito This manuscript is an update to the earlier Science of Synthesis contribution describing methods for the preparation of aluminum halides used for organic synthesis, along with recent synthetic applications of aluminum halides. N H N Me H Et 2 AlCl, toluene 0 o C to rt 93% Me N N Al Cl Keywords: acid catalysts aluminum compounds bromides chiral compounds chlorides halides iodides ionic liquids Lewis acid catalysts salen complexes 2010 Updated Section 2010 Completely Revised Contributions New New Contributions

13 X Science of Synthesis Abstracts 2010 p Triorganoaluminum Compounds M. ishi and H. Takikawa This manuscript is an update to the earlier Science of Synthesis contribution describing applications of triorganoaluminums and related compounds. It focuses on selective carboalumination, catalytic enantioselective conjugate additions, and carbonyl additions covered in the literature over the period In addition, activations of C-F and C-H bonds are of increasing importance in organoaluminum chemistry. Pr i 1. 5 mol% Cl Zr Cl Pr i Me 3 Al, MA diastereomer separation H 79%; dr 40:1; 98% ee 90% ee H siphonarienal CH MA = methylaluminoxane Keywords: carboalumination carbonyl additions conjugate addition reactions coupling reactions regioselectivity enantioselectivity C-H bond activation C-F bond activation 2010 p Gallium Compounds M. Yamaguchi This manuscript is an update to the earlier Science of Synthesis contribution describing methods for the synthesis of organogallium compounds as well as their application in organic synthesis. It focuses on the literature published in the period GaCl 3 (0.25 equiv) Pr i 91% CN Pr i NC Keywords: catalysis complexation gallium compounds Lewis acid catalysts metal alkyl complexes organometallic reagents oxidative addition 2010 Updated Section 2010 Completely Revised Contributions New New Contributions

14 Abstracts XI 2010 p Product Class 3: Indium Compounds S. Araki and T. Hirashita This manuscript is a revision update to the earlier Science of Synthesis contribution describing methods for the synthesis of indium compounds. More recent developments in this area, in particular chemical transformations using indium reagents, have been reviewed. R 1 R 2 R 1 R 2 H X + In InL n R 1 N R 2 R 2 NH R 1 R 1 R 2 R 1 R 2 Keywords: allylic compounds allenic compounds allylation Barbier reaction carbon-metal bonds carbon carbon coupling reactions indium compounds Lewis acid catalysts transmetalation 2010 p Barium Compounds A. Yanagisawa This manuscript is an update to the earlier Science of Synthesis contribution describing methods for the application of barium compounds in organic synthesis. It focuses on the literature published in the decade up to mol% H H Bn 2 C + H 10 mol% Ba(iPr) 2 DME, 0 o C, 24 h 85% (2 equiv) H H Bn 2 C R + Bn 2 C 99% ee >20:1 Keywords: aldol reaction b-amino carbonyl compounds asymmetric catalysis barium compounds conjugate addition cross-coupling reactions Diels Alder reaction 1,5-di Updated Section 2010 Completely Revised Contributions New New Contributions

15 XII Science of Synthesis Abstracts ketones homocoupling b-hydroxy carbonyl compounds Mannich-type reaction propargylic compounds New p The Catalytic Use of Lithium Compounds for Bond Formation S. Matsunaga The catalytic use of lithium compounds as Lewis bases and Brønsted bases is introduced. Several C-C bond-forming (enantioselective) transformations, such as aldol reactions, Mannich reactions, cyanation, conjugate additions, sulfur ylide additions for oxirane and oxetane synthesis, and others, are described. H + TMSCN 10 mol% (R)-BINL 10 mol% LiiPr toluene, 78 o C, 1 h 96%; 98% ee TMS CN Keywords: asymmetric aldol reaction asymmetric Mannich reaction asymmetric cyanation lithium compounds Lewis base catalysts asymmetric conjugate addition reactions asymmetric Michael reaction sulfur ylides oxetane oxiranes Brønsted base catalysts New p The Catalytic Use of Sodium Compounds for Bond Formation T. Arai Safe and inexpensive sodium reagents are promoted as versatile Lewis base, Lewis acid, and combination acid base catalysts in green chemistry. Sodium-containing heterobimetallic asymmetric complexes enable highly stereoselective catalysis of transformations such as Michael reactions, cyclopropanation, and the Henry reaction. TMS TMS CN Cl 3 C TMS sodium catalysis: safe and inexpensive H Bn N 2 EtS S C 2 Bn C 2 Bn Keywords: sodium compounds catalysis asymmetric synthesis Mukaiyama reaction Michael reaction 2010 Updated Section 2010 Completely Revised Contributions New New Contributions