In recent years a great deal of research has been applied to homogeneous hydrogenation with non-precious catalysis. Homogeneous Hydrogenation with Non-Precious Catalysts offers a review of the latest developments and advances in the field. In addition, the book explores the transition metal catalysis and the concept of frustrated-lewis-pair (FLP) and enzymatic processes. The editor?a noted expert on the topic?discusses the various catalysts and puts the focus on the synthetic vantage point, highlighting the functional group transformation enabled by the respective catalyst.
Homogeneous Hydrogenation with Non-Precious Catalysts also presents the industrial view of the topic and includes an overview of the various catalysts by functional group transformations. This important book:
-Offers a comprehensive presentation of the newest development in this emerging field
-Highlights the transition metal catalysis, the frustrated-lewis-pair (FLP) concept, and enzymatic processes
-Provides an industrial perspective of the topic
-Includes an overview of the various catalysis by functional group transformations
Written for organic chemists, researchers in synthetic chemistry, and industry professionals, Homogeneous Hydrogenation with Non-Precious Catalysts offers a comprehensive and accessible guide to the most recent advances in the field.
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Table of Contents
Preface ix
Prelude - A Critical Assessment from an Industrial Point of View 1
Hans-Ulrich Blaser
1 Some Introductory Remarks 1
1.1 What is the Motivation for Developing Non-Noble Metal Catalysts? 2
1.2 Crucial Parameters for Process Development 3
1.2.1 The Catalyst: Metal Complex, (Chiral) Ligand 4
1.2.2 The Process 5
2 Comparison with the Established Catalysts 5
2.1 Chemoselective Hydrogenations: Alternatives to Heterogeneous Catalysts 6
2.1.1 Hydrogenation of Esters 6
2.1.2 E-Selective Hydrogenation of Alkynes 7
2.1.3 Selective C=O Reduction of Unsaturated Carbonyl Groups 7
2.2 Enantioselective Hydrogenations 8
2.3 A Few Remarkable Transformations Using Cu and Co Complexes 9
3 Epilogue 10
References 13
1 Iron-Catalyzed Homogeneous Hydrogenation Reactions 15
Thomas Zell and Robert Langer
1.1 Introduction 15
1.2 Fundamental Differences Between Noble and 3dMetal Complexes 17
1.3 Mechanistic Scenarios and the Role of Substrates 22
1.3.1 Nonpolar Substrates 22
1.3.2 Polar Substrates 24
1.3.3 Exceptions 25
1.4 Iron-Catalyzed Hydrogenation of C - C Multiple Bonds 26
1.4.1 Hydrogenation of Olefins 26
1.4.2 Hydrogenation of Alkynes 27
1.5 Iron-Catalyzed Hydrogenation of C - O Multiple Bonds 28
1.5.1 Hydrogenation of Aldehydes and Ketones 29
1.5.2 Hydrogenation of Esters 31
1.5.3 Hydrogenation of Amides 32
1.6 Iron-Catalyzed Hydrogenation of C - N Multiple Bonds 32
1.7 Conclusion 34
Abbreviations 35
References 35
2 Cobalt-Catalyzed Hydrogenations 39
Felicia Weber and Gerhard Hilt
2.1 Introduction 39
2.2 Hydrogenation Reactions 39
2.2.1 Activation of Molecular Hydrogen-Dihydrogen Complexes vs. Dihydride Complexes 39
2.2.2 Hydrogenation of CO2, Carboxylic Acids, Carboxylic Esters, and Nitriles 40
2.2.3 Hydrogenation of C=O, C=N, C=C, C≡C, and (Hetero)arenes 46
2.3 Conclusion 57
References 57
3 Homogeneous Nickel-Catalyzed Hydrogenations 63
Marlene Böldl and Ivana Fleischer
3.1 Introduction 63
3.2 Hydrogenation of Alkenes 65
3.2.1 Hydrogenation of Alkyl- and Aryl-Substituted Alkenes 65
3.2.2 Hydrogenation of Electron-Deficient Alkenes 76
3.3 Hydrogenation of Alkynes 78
3.4 Hydrogenation of Carbonyl Groups 79
3.4.1 Hydrogenation of Ketones 79
3.4.2 Hydrogenation of Carbon Dioxide 81
3.5 Conclusions 83
References 83
4 Homogeneous Hydrogenation with Copper Catalysts 87
Niklas O. Thiel, Felix Pape, and Johannes F. Teichert
4.1 Introduction 87
4.1.1 Early Studies on Copper-Catalyzed Hydrogenations 87
4.2 Hydrogenation of (α,β-Unsaturated) Carbonyl and Carboxyl Compounds 88
4.2.1 Conjugate Reduction 88
4.2.2 1,2-Hydrogenation of α,β-Unsaturated Ketones and Aldehydes 91
4.2.3 Asymmetric 1,2-Hydrogenation of Simple (Nonconjugated) Ketones and Aldehydes 92
4.3 CO2 Reduction to Formate 93
4.4 Allylic Substitutions with a Hydride Nucleophile Generated from H2 95
4.5 Z-Selective Alkyne Semihydrogenation 98
4.6 Alkyne Transfer Semihydrogenation and Transfer Conjugate Reduction with Ammonia Borane 104
4.7 Dihydrogen-Mediated Cross-Coupling of Internal Alkynes and Aryl iodides 105
4.8 Conclusions and Perspectives 106
References 107
5 Hydrogenation Reactions Using Group III to Group VII Transition Metals 111
Matthew L. Clarke and Magnus B. Widegren
5.1 Introduction 111
5.2 Group III Metals: Scandium and Yttrium 111
5.3 Group IV Metals: Titanium, Zirconium, and Hafnium 112
5.3.1 Asymmetric Hydrogenation Using Titanium and Zirconium Catalysts 115
5.4 Group V Metals: Vanadium, Niobium, and Tantalum 119
5.5 Group VI Metals: Chromium, Molybdenum, and Tungsten 121
5.6 Group VII Metals: Manganese and Rhenium 122
5.7 Summary and Conclusions 137
References 137
6 Early Main Group Metal Catalyzed Hydrogenation 141
Heiko Bauer and Sjoerd Harder
6.1 Introduction 141
6.2 Hydrogenation of C=C Double Bonds 144
6.3 Hydrogenation of C=N Double Bonds 153
6.4 Hydrogenation of C=O Double Bonds 157
6.5 Summary and Perspectives 160
References 163
7 Frustrated Lewis Pair-Catalyzed Reductions Using Molecular Hydrogen 167
Jan Paradies and Sebastian Tussing
7.1 Introduction 167
7.2 Mechanistic Considerations 168
7.3 Influence of the Lewis Acid and Lewis Base on Hydrogenation Reactivity 171
7.3.1 Choice of Lewis Acid 172
7.4 Balance Between Lewis Acidity and Lewis Basicity 173
7.4.1 Hydrogenation of Olefins 178
7.4.2 Dehydrogenative Coupling 179
7.4.3 Acceptorless Dehydrogenation 180
7.4.4 Intramolecular Frustrated Lewis Pairs 181
7.4.5 Air-Stable FLPs 184
7.5 Application of Frustrated Lewis Pairs in Hydrogenations 187
7.5.1 Hydrogenation of Aldimines and Ketimines 187
7.5.2 Hydrogenation of Enamines and Silylenol Ethers 193
7.5.3 Hydrogenation of Ketones 198
7.5.4 Reductive Deoxygenations 198
7.6 Hydrogenation of Heterocycles 201
7.7 Hydrogenation of Enones, Alkylidene Malonates, and Nitroolefins 207
7.8 Hydrogenation of Unpolarized Olefins and Polycyclic Aromatic Hydrocarbons 211
7.9 Electrophilic Phosphonium Cations (EPCs) 215
7.10 Summary 217
Abbreviations 217
References 218
8 Recent Advances in Selective Biocatalytic (Hydrogen Transfer) Reductions 227
Gonzalo de Gonzalo and Iván Lavandera
8.1 Introduction 227
8.2 Ketoreductases 228
8.2.1 Alcohol Dehydrogenases in “Nonconventional”Media 229
8.2.2 Dynamic Processes Employing Ketoreductases 230
8.2.3 Alcohol Dehydrogenases in Multicatalytic Processes 232
8.2.4 Application of Ketoreductases to the Synthesis of Valuable Compounds 236
8.3 Ene-Reductases 241
8.3.1 Substrate Scope of Ene-Reductases 242
8.3.2 Ene-Reductases in Multicatalytic Processes 244
8.4 Imine Reductases 248
8.5 Carboxylic Acid Reductases 249
8.6 Emerging Enzymes: Nitrile Reductases and Nitroreductases 250
8.7 Summary and Outlook 251
Abbreviations 252
References 253
9 Organocatalytic Transfer Hydrogenation 261
Jie Wang and Yong-Gui Zhou
9.1 Introduction 261
9.2 Asymmetric Transfer Hydrogenation of C=C Bonds 262
9.3 Asymmetric Transfer Hydrogenation of C=N Bonds 266
9.4 Asymmetric Transfer Hydrogenation of C=O Bonds 273
9.5 Asymmetric Transfer Hydrogenation of Heteroaromatics 274
9.6 Summary and Outlook 280
Abbreviations 280
References 281
Index 285
