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Handbook of C-H Transformations [organic chemistry PDF

679 Pages·2005·5.18 MB·English
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Handbook of C±H Transformations Volume 1 Edited by Gerald Dyker Handbook of C±H Transformations. Gerald Dyker (Ed.) Copyright 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-31074-6 Further Titles of Interest R. Mahrwald (Ed.) Modern Aldol Reactions 2004, ISBN 3-527-30714-1 A. de Meijere, F. Diederich (Eds.) Metal-Catalyzed Cross-Coupling Reactions 2 Vols. 2004, ISBN 3-527-30518-1 M. Beller, C. Bolm (Eds.) Transition Metals for Organic Synthesis 2004, ISBN 3-527-30613-7 K. C. Nicolaou, S. A. Snyder (Eds.) Classics in Total Synthesis II 2003, ISBN 3-527-30685-4 M. M. Green, H. A. Wittcroft Organic Chemistry Principles and Industrial Practice 2003, ISBN 3-527-30289-1 C. Reichardt Solvent and Solvent Effects in Organic Chemistry 2003, ISBn 3-527-30618-8 Handbook of C±H Transformations Applications in Organic Synthesis Volume 1 Edited by Gerald Dyker Editors & All books published by Wiley-VCH are carefully produced. Nevertheless, authors, Prof. Gerald Dyker editors, and publisher do not warrant the Department of Chemistry information contained in these books, BochumUniversity including this book, to be free of errors. 44780 Bochum Readers are advised to keep in mind that Germany statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. 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>. 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form± 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 considered unprotected by law. Printed in the Federal Republic of Germany. Printed on acid-free paper. Typesetting Kühn & Weyh, Satz und Medien, Freiburg Printing betz-druck GmbH, Darmstadt Bookbinding J. Schäffer GmbH, Grünstadt ISBN-13: 978-3-527-31074-6 ISBN-10: 3-527-31074-6 V Preface The direct transformation of C-H bonds is a fundamental task in organic synthe- sis, regularly facing reactivity and selectivity problems but simultaneously promis- ing substantial benefits. The intention of this handbook, written by renowned authors who have contributed substantially to this research area, is to present, very concisely within its 66 sections, the whole range of modern methods for C-H- transformation. Most of the sections follow a general concept and are therefore divided into five parts which cover the most important features of the reaction in focus. ªIntroduc- tion and Fundamental Examplesº gives general information about the reaction, especially the scientific background and related reactions. This part also includes reactions which might be important to understanding although not necessarily of preparative value. ªMechanismº presents current mechanistic considerations, eventually including critical remarks. ªScope and Limitationsº concentrates on examples which lead to interesting structures, usually with yields in excess of 50%. ªExperimentalº presents instructive, comprehensible examples, including work-up procedures. Information about appropriate methods for monitoring the reaction (TLC data or diagnostic NMR spectroscopy) are also given. If a special catalyst is needed, the procedure for its synthesis is also included. ªReferences and Notesº, of course, leads to significant publications where further details are available. You may notice that this preface is as concise as the contents of this handbook. Nevertheless, as editor I should not forget to thankall authors and the team from Wiley-VCH, who made this project possible. The transformation of C-H bonds is certainly one of the most important fields of research in preparative organic chemistry; let us hope this handbookwill further motivate research, simulta- neously accelerating the change from new developments to established synthetic tools. Gerald Dyker Bochum, April 2005 Handbook of C±H Transformations. Gerald Dyker (Ed.) Copyright 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-31074-6 VII Contents Volume 1 Preface V List of Contributors XVII I General 1 1 What is C±H Bond Activation? 3 Bengü Sezen and Dalibor Sames 1.1 Introduction 3 1.2 Activation or ªActivationº 3 1.3 The Origin and Historical Context of the ªOrganometallic Definitionº 4 1.4What Do We Do With Two Definitions? 6 1.5 Conclusions 9 2 C±H Transformation in Industrial Processes 11 Leslaw Mleczko, Sigurd Buchholz, Christian Münnich 2.1 Introduction 11 2.2 Alkane Activation 11 2.3 C±H Transformation at Olefins 17 2.4Basic Chemicals from Aromatic Hydrocarbons 19 2.5 Fine Chemicals 22 2.5.1 Fine Chemicals by Organometallic Catalysis 23 2.5.2 Metal-free Synthesis of Fine Chemicals 24 Handbook of C±H Transformations. Gerald Dyker (Ed.) Copyright 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-31074-6 VIII Contents II C±H Transformation at sp-Hybridized Carbon Atoms 29 1 C±H Transformation at Terminal Alkynes 31 1.1 Recent Developments in Enantioselective Addition of Terminal Alkynes to Aldehydes 31 Tobias Ritter and Erick M. Carreira 1.1.1 Introduction 31 1.1.2 Background 32 1.1.3 Enantioselective Addition of Terminal Alkenes to Aldehydes 33 1.1.4Applications 37 1.1.5 Conclusion 42 Experimental 42 1.2 The Sonogashira Coupling Reaction 45 Herbert Plenio and Anupama Datta 1.2.1 Introduction and Fundamental Examples 45 1.2.2 Mechanism 46 1.2.3 Scope and Limitations 48 1.3 Glaser Homocoupling and the Cadiot±Chodkiewicz Heterocoupling Reaction 53 Peter Siemsen and Beatrice Felber 1.3.1 Introduction and Fundamental Examples 53 1.3.2 Mechanism 56 1.3.2.1 Oxidative Homocoupling 56 1.3.2.2 Nonoxidative Heterocoupling 57 1.3.3 Scope and Limitations 58 1.3.3.1 Oxidative Homocouplings of Tetraethynylethene Derivatives 58 1.3.3.2 Nonoxidative Heterocoupling of Terminal Alkynes with Haloalkynes: Cadiot±Chodkiewicz Reaction 60 1.4Dimerization of Terminal Alkynes 62 Emilio Bustelo and Pierre H. Dixneuf 1.4.1 Introduction and fundamental examples 62 1.4.1.1 Simple Dimerization of Alkynes 62 1.4.1.2 Dimerization of Alkynes and Propargyl Alcohols into Functional Dienes or Cyclobutenes 66 1.5 anti-Markovnikov Addition to Terminal Alkynes via Ruthenium Vinylidene Intermediates 72 Christian Bruneau 1.5.1 Introduction 72 1.5.2 Application to the Synthesis of Vinylcarbamates 73 1.5.3 Application to the Synthesis of Enol Esters 73 1.5.4Application to the Isomerization of Propargylic Alcohols 75 1.5.5 Application to the Synthesis of Vinylic Ethers 76 1.5.6 Application to the Synthesis of Unsaturated Ketones 76 1.5.7 Application to the Synthesis of Cyclic Enol Ethers and Lactones 77 Contents IX 1.5.8 Application to the Synthesis of Aldehydes 78 1.5.9 Scope and Limitations 78 2 Asymmetric Hydrocyanation of Alkenes 87 Jos Wilting and Dieter Vogt 2.1 Introduction 87 2.1.1 Cyclic (Di)enes 88 2.1.2 Vinylarenes 88 2.2 Mechanism 89 2.3 Scope and Limitations 92 2 III C±H Transformation at sp -hybridized Carbon Atoms 97 1 C±H Transformation at Arenes 99 1.1 Direct Oxidation of Arenes to Phenols and Quinones 99 Vsevolod V. Rostovtsev 1.1.1 Introduction 99 1.1.2 Radical Hydroxylations 99 1.1.3 Electrophilic Hydroxylations 102 1.1.4Nucleophilic Hydroxylations 104 1.1.5 Direct Synthesis of Quinones from Arenes 105 1.2 Metalation of Arenes 106 1.2.1 Directed ortho and Remote Metalation (DoM and DreM) 106 Victor Snieckus and T. Macklin 1.2.1.1 Introduction and Fundamental Concepts 106 1.2.1.2 Mechanism 110 1.2.1.3 Scope and Limitations 112 1.2.1.4DoM Methodology for Substituted Aromatics 113 1.2.1.5 DoM in Total Synthesis 115 1.2.2 Electrophilic Metalation of Arenes 119 Vladimir V. Grushin 1.2.2.1 Introduction 119 1.2.2.2 Mercuration 119 1.2.2.3 Thallation 121 1.2.2.4Plumbylation (Plumbation) 122 1.2.2.5 Stannylation 124 1.2.3 Iridium-Catalyzed Borylation of Arenes 126 Tatsuo Ishiyama and Norio Miyaura 1.2.3.1 Introduction and Fundamental Examples 126 1.2.3.2 Mechanism 128 1.2.3.3 Scope and Limitations 129 1.2.4Transition-metal Catalyzed Silylation of Arenes 131 Fumitoshi Kakiuchi X Contents 1.2.4.1 Introduction and Fundamentals 131 1.2.4.2 Mechanism 133 1.2.4.3 Scope and Limitations 133 1.3 Alkylation and Vinylation of Arenes 137 1.3.1 Friedel±Crafts-type Reactions 137 1.3.1.1 Comparison of Classical and Fancy Catalysts in Friedel±Crafts-type Reactions 137 Gerald Dyker 1.3.1.2 Lanthanoid Triflates in Catalytic Amounts for Friedel±Crafts-type Reactions 142 Shu Kobayashi 1.3.1.3 Enantioselective Friedel±Crafts Type Alkylation Reactions 150 Marco Bandini, Alfonso Melloni, and Fabio Piccinelli 1.3.1.4Gold-catalyzed Hydroarylation of Alkynes 157 Manfred T. Reetz and Knut Sommer 1.3.2 Alkylation and Vinylation via Intermediary Transition Metal r-Complexes of Arenes 166 1.3.2.1 Ruthenium-catalyzed ortho-Activation of Carbonyl-substituted Arenes 166 Fumitoshi Kakiuchi and Shinji Murai 1.3.2.2 Ruthenium-Catalyzed alpha-Activation of Heteroarenes 175 Naoto Chatani 1.3.2.3 Ruthenium(II)- and Iridium(III)-catalyzed Addition of Aromatic C±H Bonds to Olefins 180 T. Brent Gunnoe and Roy A. Periana 1.3.2.4Catalytic Functionalization of N-Heterocycles via their Rhodium±Carbene Complexes 187 Sean H. Wiedemann, Jonathan A. Ellman, and Robert G. Bergman 1.3.2.5 Fujiwara Reaction: Palladium-catalyzed Hydroarylations of Alkynes and Alkenes 194 Yuzo Fujiwara and Tsugio Kitamura 1.3.2.6 Palladium-catalyzed Oxidative Vinylation 203 Piet W. N. M. van Leeuwen and Johannes G. de Vries 1.3.3 Minisci Radical Alkylation and Acylation 212 Ombretta Porta and Francesco Minisci 1.3.3.1 Introduction 212 1.3.3.2 Mechanism 213 1.3.3.3 Scope, Limitations and Fundamental Examples 214 1.4Aryl±Aryl Coupling Reactions 223 1.4.1 Intermolecular Arylation Reactions 223 1.4.1.1 Intermolecular Arylation Reactions of Phenols and Aromatic Carbonyl Compounds 223 Masahiro Miura and Tetsuya Satoh

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