Discover the latest developments in homogeneous asymmetric (transfer) hydrogenation with this up-to-date resource
Asymmetric Hydrogenation and Transfer Hydrogenation delivers a current and cutting-edge investigation of homogenous asymmetric hydrogenation and transfer hydrogenation reactions of prochiral substrates by using organometallic catalysts (like ruthenium, rhodium, iridium, iron, and copper) and organic catalysts.
Distinguished researchers and editors Virginie Ratovelomanana-Vidal and Phannarath Phansavath also offer readers a comprehensive walkthrough of substituted ketones through dynamic kinetic resolution, as well a presentation of the mechanisms and application of asymmetric hydrogenation reactions to the synthesis of biologically relevant compounds.
The book comprehensively details its complex subject matter clearly and plainly and covers everything from catalyst development and reactions to mechanisms and applications in academia and industry. The papers included within come from many of the leading voices in their respective fields and represent the newest and best research available today.
Compiled for researchers and private-industry chemists alike, Asymmetric Hydrogenation and Transfer Hydrogenation also discusses a wide variety of other topics like:- A discussion of the development of chiral metal catalysts for asymmetric transfer hydrogenation- Several examinations of asymmetric transfer hydrogenation of a variety of chemical groups, including ketones, aryl and heteroaryl ketones, substituted ketones, and heteroaromatic compounds, alkenes, and imines- An exploration of the mechanism of asymmetric hydrogenation and continuous flow asymmetric hydrogenation- A full and thorough treatment of the industrial applications of asymmetric hydrogenation
Perfect for catalytic chemists, chemists working on or with organometallics, organic chemists, natural product chemists, pharmaceutical chemists, medicinal chemists, and industrial chemists, Asymmetric Hydrogenation and Transfer Hydrogenation also belongs on the bookshelves of research and university institutes and libraries who wish to expand their selection on a topic fundamental to organic synthesis.
Table of Contents
Foreword xi
Preface xiii
1 The Historical Development of Asymmetric Hydrogenation 1
John M. Brown
1.1 Introduction 1
1.2 Early Work on the Recognition of Molecular Asymmetry 1
1.3 Origins and Early Development of Asymmetric Synthesis 4
1.4 Early Developments in the Asymmetric Heterogeneous Hydrogenation of Alkenes 8
1.5 The Development of Rhodium Asymmetric Homogeneous Hydrogenation of Alkenes 10
1.6 The Development of Ruthenium Asymmetric Homogeneous Hydrogenation of Alkenes 16
1.7 Conclusions 18
References 19
2 Asymmetric (Transfer) Hydrogenation of Functionalized Alkenes During the Past Decade 25
Christian Bruneau
2.1 Introduction 25
2.2 Asymmetric Hydrogenation with Rhodium Catalysts 25
2.2.1 Chiral Bisphosphine Ligands 25
2.2.2 Chiral Ferrocenyl Bisphosphine Ligands 27
2.2.3 Chiral Phosphine-Phosphoramidite and Phosphine-Phosphite Ligands 31
2.2.4 Self-assembled Diphosphine Ligands 33
2.2.5 Monodentate Phosphorus Ligands 33
2.2.6 Asymmetric Transfer Hydrogenation with Rhodium Catalysts 34
2.3 Asymmetric Hydrogenation with Iridium Catalysts 36
2.3.1 Chiral Bidentate Ferrocenyl Ligands 36
2.3.2 Other Chiral Bidentate P,N-ligands 37
2.3.3 Asymmetric Transfer Hydrogenation with Iridium Catalysts 42
2.4 Asymmetric Hydrogenation with Other Transition Metal Catalysts 43
2.4.1 Asymmetric Hydrogenation with Ruthenium Catalysts 43
2.4.2 Asymmetric Hydrogenation with Palladium Catalysts 46
2.5 Asymmetric (Transfer) Hydrogenation with First-row Transition Metal Catalysts 48
2.6 Conclusion 48
References 49
3 Asymmetric (Transfer) Hydrogenation of Functionalized Ketones 55
Noriyoshi Arai and Takeshi Ohkuma
3.1 Introduction 55
3.2 Asymmetric (Transfer) Hydrogenation of Alkyl Ketones 57
3.3 Asymmetric Hydrogenation of α,β-Unsaturated Ketones 66
3.3.1 Alkenyl Alkyl Ketones 66
3.3.2 Alkynyl Alkyl Ketones 71
3.4 Asymmetric Hydrogenation of α-Aminoketones 73
3.5 Asymmetric Hydrogenation of α-hydroxyketones 77
3.6 Asymmetric Hydrogenation of α-Oxophosphonates 80
3.7 Summary and Conclusions 83
References 83
4 Asymmetric (Transfer) Hydrogenation of Aryl and Heteroaryl Ketones 87
Jian-Hua Xie and Qi-Lin Zhou
4.1 Introduction 87
4.2 Asymmetric Hydrogenation of Aryl and Heteroaryl Ketones 88
4.2.1 Chiral Ruthenium Catalysts 90
4.2.1.1 Chiral Ruthenium-Diphosphine/Diamine Catalysts 90
4.2.1.2 Chiral Arene-Ruthenium-Diamine Catalysts 95
4.2.1.3 Chiral Ruthenium-Phosphine-Oxazoline Catalysts 96
4.2.1.4 Chiral Ruthenium Catalysts Containing Tridentate Pincer Ligands 97
4.2.1.5 Chiral Ruthenium Catalysts Containing Tetradentate Ligands 98
4.2.2 Chiral Iridium Catalysts 98
4.2.3 Other Chiral Metal Catalysts 100
4.3 Asymmetric Transfer Hydrogenation of Aryl and Heteroaryl Ketones 103
4.3.1 Chiral Ruthenium Catalysts 104
4.3.1.1 Chiral Arene Ruthenium-N-Sulfonylated 1,2-Diamine Complexes 104
4.3.1.2 Chiral Ruthenium Catalysts with Other Bidentate Ligands 107
4.3.1.3 Chiral Ruthenium Catalysts Containing Tridentate and Tetradentate Ligands 111
4.3.2 Chiral Rhodium and Iridium Catalysts 112
4.3.2.1 Chiral Rhodium and Iridium Complexes Containing Diamine and Related Ligands 113
4.3.2.2 Chiral Rhodium and Iridium Catalysts Containing Other Ligands 116
4.3.3 Other Chiral Metal Catalysts 117
4.3.3.1 Chiral Iron Catalysts 118
4.3.3.2 Chiral Osmium Catalysts 119
4.3.3.3 Other Chiral Metal Catalysts 119
4.4 Summary 120
References 121
5 Asymmetric (Transfer) Hydrogenation of Substituted Ketones Through Dynamic Kinetic Resolution 129
Pierre-Georges Echeverria, Tahar Ayad, Phannarath Phansavath and Virginie Ratovelomanana-Vidal
5.1 Introduction 129
5.2 α-Substituted Ketones 130
5.3 α-Substituted Cyclic Ketones 135
5.4 α,α′-Disubstituted Cyclic Ketones 142
5.5 α,β-Disubstituted Cyclic Ketones 143
5.6 α-Substituted β-Keto Esters 144
5.6.1 α-Amino β-Keto Esters 144
5.6.2 Other α-Substituted β-Keto Esters 151
5.7 α-Substituted β-Keto Amides 156
5.8 α-Substituted β-Keto Sulfones, Sulfonamides, and Phosphonates 160
5.9 β-Substituted α-Keto Esters and Phosphonates 163
5.10 β-Alkoxy Ketones 166
5.11 1,2-Diketones 167
5.12 β-Substituted Ketones 167
5.13 α-Substituted Aldehydes 168
5.14 Summary and Conclusions 169
References 169
6 Industrial Applications of Asymmetric (Transfer) Hydrogenation 175
Xumu Zhang and Pan-Lin Shao
6.1 Introduction 175
6.2 Industrial Applications of Asymmetric Hydrogenation 177
6.2.1 Asymmetric Hydrogenation of Enamide 177
6.2.1.1 L-DOPA 177
6.2.1.2 Ramipril 178
6.2.1.3 Sitagliptin 179
6.2.1.4 (R)-3-Amino-1-butanol 181
6.2.1.5 (S)-2,6-Dimethyltyrosine 182
6.2.1.6 Apremilast 184
6.2.2 Asymmetric Hydrogenation of Ketone 185
6.2.2.1 Duloxetine 185
6.2.2.2 Dorzolamide 186
6.2.2.3 (R)-1-(3,5-Bis(trifluoromethyl)-phenyl)ethanol 187
6.2.2.4 4-AA (Key Intermediate to Carbapenem Antibiotics) 189
6.2.2.5 Rivastigmine 190
6.2.2.6 Montelukast 191
6.2.2.7 Crizotinib 192
6.2.2.8 (R)-Phenylephrine 194
6.2.2.9 Atorvastatin Calcium Salt 197
6.2.2.10 Orlistat 198
6.2.2.11 Ezetimibe 199
6.2.3 Asymmetric Hydrogenation of Olefin 201
6.2.3.1 L-Menthol 201
6.2.3.2 Sacubitril 202
6.2.3.3 Naproxen, Ibuprofen, and Flurbiprofen 204
6.2.3.4 Ramelteon 205
6.2.3.5 Aliskiren 205
6.2.3.6 (+)-cis-Methyl Dihydrojasmonate 207
6.2.4 Asymmetric Hydrogenation of Imine 209
6.2.4.1 Solifenacin 209
6.2.4.2 (S)-Metolachlor 210
6.2.5 Asymmetric Transfer Hydrogenation 211
6.3 Summary and Conclusions 212
References 212
7 Tethered Ruthenium(II) Catalysts in Asymmetric Transfer Hydrogenation 221
Vijyesh K. Vyas, Richard C. Knighton and Martin Wills
7.1 Introduction: The Rationale Behind Tethered Catalysts Design 221
7.2 Tethered Ru(II) Catalysts and Their Syntheses 222
7.2.1 Synthetic Approaches to Tethered Catalysts 224
7.3 Applications to Asymmetric Reductions of Ketones and Imines 226
7.3.1 Reductions of Acetophenone Derivatives 226
7.3.1.1 Asymmetric Transfer Hydrogenation Using Formic Acid 228
7.3.1.2 Reduction Under Aqueous Conditions 231
7.3.1.3 Hydrogenation with Hydrogen Gas 232
7.3.1.4 Racemic Catalysts for Reductions 232
7.3.1.5 Specific Applications to Complex Acetophenone Derivatives 232
7.3.2 Reductions of Acetylenic Ketones 235
7.3.3 Reductions of Benzophenone Ketones 235
7.3.4 Reductions of Diverse Ketones 237
7.3.5 Dynamic Kinetic Resolutions 242
7.3.6 Reductions of Imines 247
7.4 Conclusions and Outlook 248
References 249
8 Homogeneous Asymmetric Hydrogenation of Heteroaromatic Compounds Catalyzed by Transition Metal Complexes 255
Qing-Hua Fan, Yan-Mei He and Fa-Ju Li
8.1 Introduction 255
8.2 Asymmetric Hydrogenation of Quinolines 257
8.3 Asymmetric Hydrogenation of Quinoxalines 260
8.4 Asymmetric Hydrogenation of Isoquinolines 262
8.5 Asymmetric Hydrogenation of Pyridines and Pyrazines 263
8.6 Asymmetric Hydrogenation of Indoles and Pyrroles 265
8.7 Asymmetric Hydrogenation of Heteroarenes with Multi-N-Heterocycles 268
8.8 Asymmetric Hydrogenation of Other N-Heteroarenes 270
8.9 Asymmetric Hydrogenation of O- and S-Heteroarenes 273
8.10 Summary and Conclusions 275
Acknowledgments 276
References 276
9 Asymmetric (Transfer) Hydrogenation of Imines 281
Itziar Peñafiel, Juan Mangas-Sánchez and Carmen Claver
9.1 Asymmetric Hydrogenation of Imines 281
9.1.1 Iridium Catalysts 281
9.1.1.1 (P,P) Ligands 281
9.1.1.2 (P,N) Ligands 282
9.1.1.3 P-Monodentate Ligands 286
9.1.2 Rhodium and Palladium Catalysts 287
9.2 Asymmetric Transfer Hydrogenation of Imines 288
9.2.1 Ruthenium Catalysts 289
9.2.2 Iridium and Rhodium Catalysts 290
9.2.3 Iron Catalysts 290
9.3 New Approaches 292
9.3.1 Metal Free 292
9.3.2 Biocatalytic Imine Reduction 293
9.3.2.1 Artificial Metalloenzymes 294
9.3.2.2 Imine Reductases (IREDs) 297
9.4 Summary and Conclusions 301
References 301
10 Asymmetric Hydrogenation in Continuous-Flow Conditions 307
Gergely Farkas, József Madarász and József Bakos
10.1 Introduction 307
10.2 Chirally Modified Metal Surfaces 308
10.3 Well-defined Transition-metal Complexes 314
10.3.1 Immobilized Systems 315
10.3.1.1 Covalently Anchored Ligands 315
10.3.1.2 Immobilization by the Augustine Method 316
10.3.1.3 Ionic Liquids as Matrices for Transition-metal Complex Catalysts 321
10.3.2 Homogeneous Systems 325
10.3.3 Self-supported Systems 328
10.4 Organocatalysts 329
10.5 Chiral Auxiliary-controlled Asymmetric Hydrogenation in Flow 332
10.6 Summary and Outlook 333
References 333
11 Organocatalytic Asymmetric Transfer Hydrogenation Reactions 339
Sayantani Das, Vijay N. Wakchaure and Benjamin List
11.1 Introduction 339
11.2 Reduction of C=C Double Bonds 341
11.3 Reduction of C=N Double Bonds 347
11.4 Cascade Reactions 359
11.5 Dearomatization 365
11.6 Conclusions 369
References 369
Index 375
