Main Group Metals in Organic Synthesis Edited by Hisashi Yamamoto and Koichiro Oshima Main Group Metals in Organic Synthesis. Edited by H. Yamamoto, K. Oshima Copyright © 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-30508-4 Further Titles of Interest B. Cornils and W.A. Herrmann (Eds.) Applied Homogeneous Catalysis with Organometallic Compounds A Comprehensive Handbook in Three Volumes 2002. ISBN 3-527-30434-7 I. Marek (Ed.) Titanium and Zirconium in Organic Synthesis 2000. ISBN 3-527-30428-2 K. Drauz and H. Waldmann (Eds.) Enzyme Catalysis in Organic Synthesis A Comprehensive Handbook in Three Volumes 2002. ISBN 3-527-29949-1 K.C. Nicolaou, R. Hanko and W. Hartwig (Eds.) Handbook of Combinatorial Chemistry Drugs, Catalysts, Materials (Two Volumes) 2002. ISBN 3-527-30509-2 H. Yamamoto (Ed.) Lewis Acids in Organic Synthesis A Comprehensive Handbook in Three Volumes 2000. ISBN 3-527-29579-8 Edited by Hisashi Yamamoto and Koichiro Oshima Main Group Metals in Organic Synthesis Editors Prof. Dr. Hisashi Yamamoto University of Chicago Department of Chemistry 5735 s Ellis Ave. Chicago, IL 60637 USA Prof. Dr. Koichiro Oshima Graduate School of Engineering Dept. of Material Chemistry Kyoto University Kyoto-daigaku Katsura Nishikyo-ku Kyoto 615-8510 Japan Library of Congress Card No.: Applied for. British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Bibliographic information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the Internet at <http://dnb.ddb.de> © 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany All rights reserved (including those of translation in other languages). No part of this book may be reproduced in any form – by photoprinting, micro- film, or any other means – nor transmitted or translated into machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be consid- ered unprotected by law. Printed in the Federal Republic of Germany Printed on acid-free paper Composition K+V Fotosatz GmbH, Beerfelden Printing Strauss Offsetdruck GmbH, Mörlenbach Bookbinding Litges & Dopf Buchbinderei GmbH, Heppenheim ISBN 3-527-30508-4 n This book was carefully produced. Nevertheless, editors, authors and publisher do not warrant the information contained therein to be free of errors. Readers are advised to keep in mind that state- ments, data, illustrations, procedural details or other items may inadvertently be inaccurate. Volume 1 Preface XVII List of Contributors XIX 1 Lithium in Organic Synthesis 1 Katsuhiko Tomooka and Masato Ito 1.1 Introduction 1 1.2 Nature of Organolithium Compounds 2 1.2.1 Overview 2 1.2.2 Structural Features 4 1.2.3 Configurational Stability 5 1.2.4 Titration of Organolithium Compounds 6 1.3 Methods for the Preparation of Organolithium Compounds 8 1.3.1 Overview 8 1.3.2 Reductive Lithiation using Lithium Metal 9 1.3.3 Preparation of Organolithium Compounds from Another Organolithium Compounds 10 1.3.3.1 Deprotonation 10 1.3.3.2 Halogen–Lithium Exchange 12 1.3.3.3 Transmetallation 13 1.3.3.4 Carbolithiation 14 1.3.3.5 Miscellaneous 16 1.4 Methods for Construction of Carbon Frameworks by Use of Organolithium Compounds 21 1.4.1 Overview 21 1.4.2 Stereospecificity 21 1.4.3 Synthetic Application 23 1.4.3.1 C–C Bond Formation: Conversion of C–Li to Halogen–Li 23 1.4.3.2 C–C Bond Formation: Conversion of C–Li to O–Li 25 1.4.3.3 C–C Bond Formation: Conversion of C–Li to N–Li 29 1.5 References 32 V Contents Main Group Metals in Organic Synthesis. Edited by H. Yamamoto, K. Oshima Copyright © 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-30508-4 2 Rubidium and Cesium in Organic Synthesis 35 Seijiro Matsubara 2.1 Introduction 35 2.2 Organo-, Silyl-, Germyl-, and Stannylmetal 35 2.3 Fluoride Ion Source 36 2.3.1 Nucleophilic Fluorination 37 2.3.2 Desilylation Reactions 37 2.3.2.1 Carbanion Equivalent Formation 38 2.3.2.2 Desilylation-Elimination 40 2.4 Electrophilic Fluorination – Cesium Fluorosulfate 41 2.5 Cesium Salts as Bases 43 2.6 Cesium Enolate 46 2.7 Catalytic Use 47 2.8 Conclusion 49 2.9 References 49 3 Magnesium in Organic Synthesis 51 Atsushi Inoue and Koichiro Oshima 3.1 Introduction 51 3.2 Preparation of Organomagnesium Compounds 52 3.2.1 Preparation from Alkyl Halides and Mg Metal 52 3.2.2 Preparation with Rieke Magnesium 54 3.2.3 Transmetalation 55 3.2.4 Sulfoxide-Magnesium Exchange (Ligand Exchange Reaction of Sulfoxides with Grignard Reagent) 56 3.2.5 Hydromagnesation 61 3.2.6 Metalation (Deprotonation from Strong Carbon Acids) 63 3.2.7 Other Preparative Methods 64 3.3 Reaction of Organomagnesium Compounds 66 3.3.1 Reaction with Organomagnesium Amides 66 3.3.1.1 Preparation of Magnesium Monoamides and Bisamides 66 3.3.1.2 Reaction with Organomagnesium Amide 67 3.3.2 Cp 2 TiCl 2 -orCp 2 ZrCl 2 -catalyzed Reaction with Grignard Reagents 72 3.3.3 Substitution at Carbon by Organomagnesium Compounds 76 3.3.4 Addition to Carbon-Carbon Multiple Bonds 83 3.3.5 Addition of Organomagnesium Compounds to Carbonyl Groups 88 3.4 Halogen-Magnesium Exchange Reactions 90 3.4.1 Practical Examples of Halogen-Magnesium Exchange Reactions 91 3.4.1.1 Perfluoro Organomagnesium Reagents] 91 3.4.1.2 Polyhalogenated Arylmagnesium Reagents 92 3.4.1.3 Exchange of Polyhalomethane Derivatives 95 3.4.1.4 Preparation of Magnesiated Nitrogen-Heterocycles 95 3.4.1.5 Formation of Enolates by Halogen-Magnesium Exchange 98 3.4.1.6 Miscellaneous Reactions 102 Contents VI 3.4.2 iPrMgBr-induced Halogen-Magnesium Exchange for the Preparation of Polyfunctional Organomagnesium Reagents 104 3.4.2.1 Exchange Reaction of Aryl Halides 104 3.4.2.2 Exchange Reaction of Heterocyclic Halides 106 3.4.2.3 Exchange Reaction of Alkenyl Halides 108 3.4.2.4 Halogen-Magnesium Exchange of Other Halides 110 3.4.2.5 Halogen-Magnesium Exchange of Resin-bound Halides 111 3.4.3 Trialkylmagnesate-induced Halogen-Magnesium Exchange Reaction 113 3.4.3.1 Iodine-Magnesium Exchange of Aryl Iodides 113 3.4.3.2 Bromine-Magnesium Exchange of Aryl Bromides 113 3.4.3.3 Halogen-Magnesium Exchange of Dihaloarenes 117 3.4.3.4 Halogen-Magnesium Exchange of Halopyridines 118 3.4.3.5 Halogen-Magnesium Exchange of Alkenyl Halides 118 3.4.4 Bromine-Magnesium Exchange of gem-Dibromo Compounds and Sub- sequent Migration of an Alkyl Group 120 3.4.4.1 Reaction of gem-Dibromocyclopropanes 120 3.4.4.2 Copper(I)-catalyzed Reaction of Dibromomethylsilanes 122 3.4.4.3 Reaction of Dibromomethylsilanes with Me 3 MgLi 123 3.4.4.4 Alkylation of Carbenoids with Grignard Reagents 123 3.5 Radical Reactions Mediated by Grignard Reagents 124 3.5.1 Cross-coupling of Alkyl Halides with Grignard Reagents 125 3.5.2 Conversion of Vicinal Methoxyiodoalkanes into (E)-Alkenes with Grignard Reagent 127 3.5.3 Radical Cyclization of b-Iodo Allylic Acetals with EtMgBr 127 3.5.4 EtMgBr-iodoalkane-mediated Coupling of Arylmagnesium Compounds with Tetrahydrofuran via a Radical Process 128 3.5.5 Mg-promoted Reductive Cross-coupling of a,b-Unsaturated Carbonyl Compounds with Aldehydes or Acyl Chlorides 131 3.6 Radical Reaction Mediated by Grignard Reagents in the Presence of Transition Metal Catalyst 134 3.6.1 Titanocene-catalyzed Double Alkylation or Double Silylation of Styrenes with Alkyl Halides or Chlorosilanes 134 3.6.2 Reaction of Grignard Reagents with Organic Halides in the Presence of Cobaltous Chloride 138 3.6.3 Cobalt-catalyzed Aryl Radical Cyclizations with Grignard Reagent 139 3.6.4 Cobalt-catalyzed Phenylative Radical Cyclization with Phenyl Grignard Reagent 140 3.6.5 Cobalt-catalyzed Heck-type Reaction of Alkyl Halides with Styrenes 142 3.6.6 Radical Cyclization of b-Halo Allylic Acetal with a Grignard Reagent in the Presence of Manganese(II) Chloride or Iron(II) Chloride 146 3.7 References 150 Contents VII 4 Calcium in Organic Synthesis 155 Jih Ru Hwu and Ke-Yung King 4.1 Introduction 155 4.2 Reductive Cleavage of Various C–O Bonds 155 4.2.1 O-Debenzylation 155 4.2.2 Cleavage of the (O=)C–OAc Single Bond 157 4.2.3 Cleavage of the R 2 N(O=C)C–O(C=O)R Single Bond 159 4.2.4 Cleavage of the C–O Bond in Dihydropyrans 160 4.2.5 Conversion of Epoxides to Alcohols 160 4.3 Reductive Cleavages of Various C–S Bonds 161 4.3.1 Desulfonylation 161 4.3.2 Cleavage of an (R 2 NCO)C–S Bond 162 4.3.3 Removal of Dithiolanes from an Allylic Position 162 4.4 Reductive Cleavage of Various C–N Bonds 163 4.4.1 Cleavage of a PhC–N Bond 163 4.4.2 Reduction of Nitriles 165 4.5 Reduction of C=C and C:C Bonds 165 4.5.1 Reduction of Alkynes 165 4.5.2 Reduction of Strained C=C Bonds 166 4.5.3 Reduction of Aryl Rings 166 4.6 Calcium Reagents in Different Forms in the Reduction of Organic Halides 167 4.7 Reductive Cleavage of an N–O Bond 168 4.8 Reduction of Various Types of Functional Group 169 4.9 Chemoselectivity and Limitation 169 4.10 Conclusions 173 4.11 Acknowledgment 173 4.12 References 173 5 Barium in Organic Synthesis 175 Akira Yanagisawa 5.1 Introduction 175 5.2 ReactiveBarium-promotedCarbon–CarbonBond-formingReactions 175 5.3 Preparation of Allylic Barium Reagents and Reactions of these Carbanions with Electrophiles 177 5.4 Other Carbon–Carbon Bond-forming Reactions Promoted by Barium Compounds 185 5.5 Summary and Conclusions 187 5.6 References 188 6 Aluminum in Organic Synthesis 189 Susumu Saito 6.1 Introduction 189 6.1.1 Natural Abundance and General Properties 190 6.1.2 Interaction of Aluminum(III) with Different Functional Groups 190 Contents VIII 6.1.2.1 Coordination and Covalent Bonds in Aluminum(III) 190 6.1.2.2 Cationic Aluminum(III): Structural and Reaction Features 192 6.1.2.3 Neutral Aluminum(III): Coordination Aptitude and Molecular Recognition 196 6.1.2.4 Other Novel Interactions Involving Neutral Aluminum(III) 203 6.1.2.5 Ligand Effect on Aluminum(III) Geometry and Interactions 206 6.2 Modern Aluminum Reagents in Selective Organic Synthesis 208 6.2.1 Carbon–Carbon Bond Formation 208 6.2.1.1 Generation and Reaction of Aluminum Enolates (Al–O–C=C Bond Formation and Reaction) 208 6.2.1.2 Aluminum–Carbonyl Complexation, Activation, and Nucleophilic Reaction 220 6.2.1.3 Strecker Reaction (Addition of CN – to C=N Bonds) 257 6.2.1.4 Carboalumination (Addition of Al–C Bonds to C=C and CC:Bonds) 258 6.2.1.5 Coupling Reactions using Transition Metals (Addition of Al–C Bonds to Other Metals and Reductive Elimination) 263 6.2.2 Reduction 264 6.2.2.1 Carbonyl Reduction (H – Addition to a C=O Bond) 265 6.2.2.2 Hydroalumination (H – Addition to C=C or CC:Bonds) 267 6.2.3 Oxidation 271 6.2.4 Rearrangement and Fragmentation 273 6.2.4.1 Beckmann Rearrangement 273 6.2.4.2 Epoxide Rearrangement 274 6.2.4.3 Claisen Rearrangement 275 6.2.4.5 Other Rearrangements and Fragmentation 278 6.2.5 Radical Initiation and Reactions 279 6.2.6 Polymerization 283 6.2.6.1 Anionic Polymerization 284 6.2.6.2 Radical Polymerization 291 6.2.6.3 Cationic Polymerization 291 6.3 Conclusion 299 6.4 References 300 7 Gallium in Organic Synthesis 307 Masahiko Yamaguchi 7.1 Use as Lewis Acids 307 7.2 Use as Bases 311 7.3 Use as Organometallic Alkylating Reagents 312 7.3.1 Carbonyl Addition Reaction 312 7.3.2 Cross-coupling Reactions 315 7.3.3 Carbometalation Reactions 316 7.4 Use as Radical Reagents 319 7.5 Use as Low Valence Reagents 320 7.6 References 321 Contents IX 8 Indium in Organic Synthesis 323 Shuki Araki and Tsunehisa Hirashita 8.1 Introduction 323 8.2 Allylation and Propargylation 324 8.2.1 Allylation and Propargylation of Carbonyl Compounds 325 8.2.1.1 Regioselectivity 325 8.2.1.2 Diastereoselectivity 327 8.2.1.3 Enantioselectivity 334 8.2.1.4 Other Allylation Reactions 335 8.2.2 Allylation and Propargylation of Compounds other than Carbonyl 338 8.2.2.1 Imines and Enamines 338 8.2.2.2 Alkenes and Alkynes 340 8.2.2.3 Other Compounds 343 8.3 Reformatsky and Other Reactions 346 8.4 Reactions in Combination with Transition-metal Catalysts 348 8.5 Reduction 354 8.5.1 Reduction of Carbonyl Groups 354 8.5.2 Reductive Coupling 356 8.5.3 Dehalogenation 358 8.5.4 Reduction of Functional Groups 360 8.6 Indium Salts as Lewis Acids 364 8.6.1 The Diels-Alder Reaction 364 8.6.2 Aldol and Mannich Reactions 366 8.6.3 Michael Addition 368 8.6.4 Friedel-Crafts Reaction 369 8.6.5 Heterocycle Synthesis 371 8.6.6 Miscellaneous Reactions 376 8.7 References 379 9 Thallium in Organic Synthesis 387 Sakae Uemura 9.1 Tl(III) Salts in Organic Synthesis 388 9.1.1 Alkene Oxidations 388 9.1.2 Ketone Oxidations 392 9.1.3 Aromatic Thallation 395 9.1.4 Aryl Couplings via One-electron Transfer 397 9.1.5 Phenol Oxidations 398 9.1.6 Miscellaneous Reactions and Catalytic Reactions 400 9.2 Tl(I) Salts in Organic Synthesis 403 9.3 References 406 Contents X [...]... Chemistry National Tsing Hua University Hsinchu Taiwan 30043 Taichi Kano Graduate School of Engineering Nagoya University Chikusa Nagoya 46 4-8 603 Japan E-mail: susumu@cc.nagoya-u.ac.jp Yoshihiro Matano Department of Molecular Engineering Graduate School of Engineering Kyoto University Kyoto-daigaku Katsura Nishikyo-ku Kyoto 61 5-8 510 Japan Main Group Metals in Organic Synthesis Edited by H Yamamoto, K Oshima... contributions Hisashi Yamamoto and Koichioro Oshima Chicago and Kyoto Main Group Metals in Organic Synthesis Edited by H Yamamoto, K Oshima Copyright © 2004 WILEY-VCH Verlag GmbH & Co KGaA, Weinheim ISBN: 3-5 2 7-3 050 8-4 XIX List of Contributors Takahiko Akiyama Department of Chemistry, Faculty of Science Gakushuin University 1-5 -1 Mejiro Toshima-ku Tokyo 17 1-8 588 Japan Atsushi Inoue Department of Material... of our forefathers, and readers are strongly recommended to Main Group Metals in Organic Synthesis Edited by H Yamamoto, K Oshima Copyright © 2004 WILEY-VCH Verlag GmbH & Co KGaA, Weinheim ISBN: 3-5 2 7-3 050 8-4 2 1 Lithium in Organic Synthesis refer to other books or reviews cited in this chapter for historical aspects and other issues regarding organolithium chemistry 1.2 Nature of Organolithium Compounds... role of Grignard reagents in organic synthesis to be even greater than first anticipated Now that we are able to understand the chemical behavior of many main- group elements such as lithium, silicon, boron, and aluminum, the purpose of this book is to summarize these recent developments and show the promising future roles of complexes of these metals in modern organic synthesis In fact, these reagents... Substitution 534 Lewis Acid-promoted Reactions Forming Silylated Products 535 Transition Metal-catalyzed Carbon–Carbon Bond Formation 537 Palladium-catalyzed Reactions 537 Rhodium-catalyzed Reactions 540 Copper-promoted Reactions 541 a-Heteroatom-substituted Organosilanes 542 Nucleophile-promoted Addition of a-Halo- and a-Thioalkylsilane 543 [3+2] Cycloadditions of Silyl-protected 1,3-Dipoles 544 Carbon–Carbon... 1.8 11 12 1 Lithium in Organic Synthesis atom functionality at a neighboring position, because the dynamic acidity of the C–H bond increases owing to intramolecular coordination of the electron-deficient lithium atom by the adjacent heteroatom Readily available alkyllithium compounds such as n-, s-, and t-BuLi are sufficiently basic for deprotonating lithiation of a wide range of organic substrates... compounds in common ethereal solvents RLi Solvent –70 8C t-BuLi DME THF ether 11 min DME THF ether 2.0 h s-BuLi n-BuLi DME THF ether PhLi ether –20 8C 0 8C 5.6 h 42 min 8h 1.0 h 1.3 h 20 h +20 8C +35 8C 2.3 h 1.8 h 153 h 10 min 31 h 2 min 1.8 h . Main Group Metals in Organic Synthesis Edited by Hisashi Yamamoto and Koichiro Oshima Main Group Metals in Organic Synthesis. Edited by H. Yamamoto, K. Oshima Copyright © 2004 WILEY-VCH. 32 V Contents Main Group Metals in Organic Synthesis. Edited by H. Yamamoto, K. Oshima Copyright © 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-5 2 7-3 050 8-4 2 Rubidium and Cesium in Organic Synthesis. 3-5 2 7-3 050 9-2 H. Yamamoto (Ed.) Lewis Acids in Organic Synthesis A Comprehensive Handbook in Three Volumes 2000. ISBN 3-5 2 7-2 957 9-8 Edited by Hisashi Yamamoto and Koichiro Oshima Main Group Metals in Organic