Handbook of C-H Transformations [organic chemistry

679 Pages·2005·5.18 MB·English

by  Gerald Dyker

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
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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.
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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
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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