- ホーム
- > 洋書
- > ドイツ書
- > Mathematics, Sciences & Technology
- > Chemistry
- > organic chemistry
基本説明
ドイツ語で出版されて好評を博した、有機金属化学の教科書の英語版。上級の学部生および大学院生対象。有機反応に加えて生体関連反応も取り扱い、触媒機構の重要な側面を詳しく論じるほか、工業的な応用などの情報も追加。各章には、自習に役立つQ&A付。
Full Description
Clearly structured and written with advanced undergraduate, graduate and PhD students in mind, this English edition of a successful German textbook not only focuses on organic reactions, but also on bio-relevant reactions. Important aspects of the catalytic mechanisms are discussed in detail while much additional information is also provided, such as industrial applications of the processes covered.
With its many questions and answers included in all chapters at different knowledge levels, this book is also ideal for self-testing before exams.
Contents
Preface xiii
Index of Frequently Used Abbreviations xv
1 Introduction 1
1.1 The Beginnings of Catalytic Research 1
1.1.1 Homogeneously Catalyzed Reactions 1
1.1.2 Heterogeneously Catalyzed Reactions 3
1.2 The Catalysis Definitions of Berzelius and Ostwald 5
1.2.1 Berzelius Catalysis Concept 5
1.2.2 Ostwalds Definition of Catalysis 6
2 Principles of Organometallic Catalysis 9
2.1 Homogeneous versus Heterogeneous Catalysis 9
2.2 Catalytic Cycles 11
2.3 Activity and Productivity of Catalysts 12
2.3.1 Catalytic Activity 12
2.3.2 Catalytic Productivity 12
2.3.3 Conversion-Time Plots 13
2.4 Selectivity and Specificity of Catalysts 14
2.5 Determination of Catalytic Mechanisms 15
2.5.1 Experimental Studies 16
2.5.2 Theoretical Studies 17
2.6 Glossary for Catalysis 18
2.7 The Development of Organometallic Catalysis 21
3 Elementary Steps in Organometallic Catalysis 27
3.1 Cleavage and Coordination of Ligands 27
3.2 Oxidative Addition and Reductive Elimination 30
3.3 Oxidative Coupling and Reductive Cleavage 35
3.4 Olefin Insertion and b-Hydrogen Elimination 37
3.5 a-Hydrogen Elimination and Carbene Insertion Reactions 40
3.6 Addition of Nucleophiles and Heterolytic Fragmentation 42
3.7 Insertion and Extrusion of CO 45
3.8 One-Electron Reduction and Oxidation 46
4 Hydrogenation of Olefins 49
4.1 Introduction 49
4.2 The Wilkinson Catalyst 50
4.2.1 Principles 50
4.2.2 Mechanism of Olefin Hydrogenation 51
4.3 Enantioselective Hydrogenation 54
4.3.1 Principles 54
4.3.2 Applications and Examples 58
4.3.2.1 Applications for Asymmetric Hydrogenation 58
4.3.2.2 Combinatorial Catalysis 59
4.3.2.3 Nonlinear Effects 61
4.3.3 Kinetically Controlled Enantioselectivity — A Closer Look 63
4.4 Dihydrogen Complexes and H 2 Activation 68
4.4.1 Dihydrogen Complexes 68
4.4.2 Activation of Dihydrogen 71
4.5 Transfer Hydrogenation 73
5 Hydroformylation of Olefins and Fischer-Tropsch Synthesis 77
5.1 Cobalt Catalysts 77
5.2 Phosphane-Modified Rhodium Catalysts 80
5.3 Enantioselective Hydroformylation 84
5.4 Significance of Hydroformylation and Outlook 88
5.4.1 Diphosphites as Ligands 89
5.4.2 Biphasic Catalysis 91
5.4.3 Synthesis of Vitamin A 93
5.4.4 Carbon Dioxide as Alternative to CO 93
5.4.5 Combinatorial and Supramolecular Catalysis 94
5.5 The Fischer-Tropsch Synthesis 95
5.5.1 Mechanism 97
6 Carbonylation of Methanol and Water-Gas Shift Reaction 101
6.1 Principles 101
6.2 The Monsanto Process 103
6.3 Synthesis of Acetic Anhydride 106
6.4 The Cativa Process 108
6.5 Water-Gas Shift Reaction and Carbon Monoxide Dehydrogenases 112
6.5.1 Water-Gas Shift Reaction 112
6.5.2 Carbon Monoxide Dehydrogenases 114
7 Metathesis 117
7.1 Metathesis of Olefins 117
7.1.1 Introduction 117
7.1.2 Mechanism 118
7.1.3 Catalysts 119
7.1.4 Mechanism - A Closer Look 123
7.1.5 Metathesis of Cycloalkenes 125
7.1.6 Metathesis of Acyclic Dienes 128
7.1.7 Enantioselective Metathesis 130
7.2 Metathesis of Alkynes 131
7.3 Enyne Metathesis 133
7.4 s-Bond Metathesis 135
7.5 Metathesis of Alkanes 137
7.5.1 Principles 137
7.5.2 Mechanism 138
7.5.3 Alkane Metathesis Via Tandem Reactions 141
8 Oligomerization of Olefins 145
8.1 Ziegler Growth Reaction 145
8.2 Nickel Effect and Nickel-Catalyzed Dimerization of Ethene 147
8.3 Trimerization of Ethene 152
8.4 Shell Higher Olefin and a-Sablin Processes 156
8.4.1 The Shell Higher Olefin Process (SHOP) 156
8.4.2 a-Sablin Process 158
8.4.3 Use of Linear a-Olefins 159
9 Polymerization of Olefins 161
9.1 Introduction 161
9.2 Ethene Polymerization 162
9.2.1 Ziegler Catalysts 162
9.2.2 Mechanism - A Closer Look 165
9.2.3 Phillips Catalysts 167
9.2.4 Polymer Types and Process Specifications 169
9.3 Propene Polymerization 171
9.3.1 Regioselectivity and Stereoselectivity 171
9.3.2 Ziegler-Natta Catalysts 175
9.3.3 Polymer Types and Process Specifications 178
9.4 Metallocene Catalysts 179
9.4.1 Cocatalysts and Anion Influence 179
9.4.2 c 2 - and c s -Symmetric Metallocene catalysts 182
9.4.2.1 Principles 182
9.4.2.2 Mechanism 184
9.4.3 Metallocene Catalysts with Diastereotopic Coordination Pockets 187
9.4.3.1 Principles 187
9.4.3.2 Hemitactic Polymers 190
9.4.3.3 Stereoblock Polymers 191
9.4.4 On the Significance of Metallocene Catalysts 191
9.5 Nonmetallocene Catalysts 193
9.5.1 Catalyst Systems of Early Transition Metals 194
9.5.2 Catalyst Systems of Late Transition Metals 194
9.5.3 Living Polymerization of Olefins and Block Copolymers 198
9.6 Copolymerization of Olefins and CO 200
9.6.1 Perfectly Alternating Copolymerization 200
9.6.2 Imperfectly Alternating Copolymerization 204
10 C-C Linkage of Dienes 207
10.1 Introduction 207
10.2 Allyl and Butadiene Complexes 208
10.2.1 Allyl Complexes 208
10.2.2 Butadiene Complexes 211
10.2.3 Re/Si and supine/prone Coordination of Allyl and Butadiene Ligands 213
10.3 Organometallic Elementary Steps of Allyl Ligands 214
10.3.1 Oxidative Coupling and Reductive Cleavage 214
10.3.2 Butadiene Insertion and b-Hydrogen Elimination 215
10.3.3 Allyl Insertion 215
10.3.4 Oxidative Addition and Reductive Elimination 216
10.3.5 anti/cis and syn/trans Correlations 218
10.4 Oligomerization and Telomerization of Butadiene 218
10.4.1 Cyclotrimerization of Butadiene 218
10.4.1.1 Mechanism 218
10.4.1.2 cis/trans Selectivity - A Closer Look 221
10.4.1.3 Industrial Synthesis of CDT 224
10.4.2 Cyclodimerization of Butadiene 224
10.4.2.1 Mechanism 224
10.4.2.2 Selectivity Control 226
10.4.3 Linear Oligomerization and Telomerization of Butadiene 230
10.5 Polymerization of Butadiene 234
10.5.1 Mechanism 234
10.5.2 Butadiene Polymerization Catalyzed by Allylnickel(II) Complexes 237
10.5.3 Synthesis and Properties of Polybutadienes and Polyisoprenes 241
11 C-C Coupling Reactions 245
11.1 Palladium-Catalyzed Cross-Coupling Reactions 245
11.1.1 Introduction 245
11.1.2 Mechanism of Cross-Coupling Reactions 246
11.1.3 Selected Types of Cross-Coupling 249
11.1.3.1 Cross-Coupling with Organolithium, Organomagnesium, and Organozinc Reagents 249
11.1.3.2 Suzuki Coupling 250
11.1.3.3 Hiyama Coupling 251
11.1.3.4 Stille Coupling 252
11.1.3.5 Sonogashira Coupling 253
11.1.3.6 Ligand Effects 254
11.1.3.7 Alkyl-Alkyl Coupling 255
11.1.3.8 Enantioselective Cross-Coupling 256
11.1.3.9 Carbonylative Cross-Coupling 258
11.2 The Heck Reaction 258
11.2.1 Mechanism of Heck Reactions 259
11.2.2 Mechanism - A Closer Look 260
11.2.3 Ligand Effects 261
11.2.4 Enantioselective Heck Reactions 263
11.3 Palladium-Catalyzed Allylic Alkylation 264
11.3.1 Principles and Mechanism 264
11.3.2 Chirality Transfer in Asymmetric Allylation 267
12 Hydrocyanation, Hydrosilylation, and Hydroamination of Olefins 271
12.1 Introduction 271
12.2 Hydrocyanation 272
12.2.1 Principles and Mechanism 272
12.2.1.1 Mechanism - A Closer Look 273
12.2.2 The DuPont Adiponitrile Process 274
12.2.3 Outlook 276
12.2.3.1 Enantioselective Hydrocyanation 276
12.2.3.2 Hydrocyanation of Alkynes 277
12.2.3.3 Hydrocyanation of Polar C¼X Bonds 278
12.3 Hydrosilylation 279
12.3.1 Principles and Mechanism 279
12.3.2 Significance of Hydrosilylation and Outlook 283
12.3.2.1 Applications 283
12.3.2.2 Enantioselective Hydrosilylation 284
12.3.2.3 Hydrosilylation of Alkynes 285
12.3.2.4 s Complexes of Silanes 286
12.4 Hydroamination 287
12.4.1 Principles 287
12.4.2 Catalyst Types 289
12.4.2.1 Alkali Metal Amides as Catalysts 289
12.4.2.2 Platinum Group Metals as Catalysts 289
12.4.2.3 Gold Complexes as Catalysts 291
12.4.2.4 Lanthanoid Complexes as Catalysts 292
13 Oxidation of Olefins and Alkanes 295
13.1 The Wacker Process 295
13.1.1 Introduction 295
13.1.2 Mechanism of Ethene Oxidation 297
13.1.3 Oxypalladation of Olefins 303
13.1.3.1 Types of Oxypalladation 303
13.1.3.2 Enantioselective Oxypalladation 305
13.1.3.3 Palladium Oxidase Catalysis 305
13.2 Epoxidation of Olefins 306
13.2.1 Introduction 306
13.2.2 Epoxidation of Ethene and Propene 307
13.2.2.1 O 2 and ROOH as Oxygen Transfer Agents 307
13.2.2.2 Mechanism 309
13.2.2.3 H 2 O 2 as Oxygen Transfer Agent 311
13.2.3 Enantioselective Oxidation of Olefins 313
13.2.3.1 Epoxidation of Allyl Alcohols 313
13.2.3.2 Epoxidation of Nonactivated Olefins 314
13.2.4 Monooxygenases 315
13.3 C-H Functionalization of Alkanes 319
13.3.1 Introduction 319
13.3.2 C-H Activation of Alkanes 319
13.3.2.1 Cyclometallation and Orthometallation 319
13.3.2.2 Intermolecular C-H Activation of Alkanes 321
13.3.3 C-H Functionalization 323
13.3.3.1 The Shilov Catalyst System 324
13.3.3.2 The Catalytica System - Hg II as Catalyst 325
13.3.3.3 The Catalytica System - Pt II as Catalyst 326
13.3.3.4 Cytochrome P- 450 326
14 Nitrogen Fixation 329
14.1 Fundamentals 329
14.2 Heterogeneously Catalyzed Nitrogen Fixation 334
14.2.1 Principles 334
14.2.2 Mechanism of Catalysis 335
14.2.3 The Industrial Catalyst 338
14.2.4 Ruthenium Catalysts 340
14.3 Enzyme-Catalyzed Nitrogen Fixation 342
14.3.1 The Fe Protein Cycle 343
14.3.2 The MoFe Protein Cycle 344
14.3.3 A Prebiotic Nitrogen-Fixing System? 347
14.4 Homogeneously Catalyzed Nitrogen Fixation 348
14.4.1 Stoichiometric Reduction of N 2 Complexes 348
14.4.2 Catalytic Reduction of Dinitrogen 352
14.4.3 Functionalization of Dinitrogen 359
Solutions to Exercises 363
Bibliography and Sources 407
References 408
Further Reading 429
Source for Structures 436
Index 439
Index of Backgrounds 456
