- ホーム
- > 洋書
- > ドイツ書
- > Mathematics, Sciences & Technology
- > Chemistry
- > organic chemistry
Full Description
Filling a gap in the market for an up-to-date work on the topic, this unique and timely book in 2 volumes is comprehensive in covering the entire range of fundamental and applied aspects of hydroformylation reactions.
The two authors are at the forefront of catalysis research, and unite here their expertise in synthetic and applied catalysis, as well as theoretical and analytical chemistry. They provide a detailed account of the catalytic systems employed, catalyst stability and recovery, mechanistic investigations, substrate scope, and technical implementation. Chapters on multiphase hydroformylation procedures, tandem hydroformylations and other industrially applied reactions using syngas and carbon monoxide are also included.
The result is a must-have reference not only for synthetic chemists working in both academic and industrial research, but also for theoreticians and analytical chemists.
Contents
Volume 1
Foreword xi
Introduction 1
References 3
1 Metals in Hydroformylation 5
1.1 The Pivotal Role of Hydrido Complexes 5
References 8
1.2 Bimetallic Catalysts 9
References 10
1.3 Effect of Organic Ligands 10
References 14
1.4 Cobalt-Catalyzed Hydroformylation 15
1.4.1 History and General Remarks 15
1.4.2 The Mechanism, Catalysts, and Ligands 16
1.4.3 Some Recent and Special Applications 20
References 23
1.5 Rhodium-Catalyzed Hydroformylation 24
1.5.1 History and Technical Importance 24
1.5.2 Catalyst Precursors 26
1.5.3 Summary and Conclusions 32
References 32
1.6 Ruthenium-Catalyzed Hydroformylation 36
1.6.1 General Aspects 36
1.6.2 Catalyst Precursors 37
1.6.3 Ligands 38
1.6.4 Mechanistic Considerations 42
1.6.5 Hydroformylation Using the Reversed Water Gas Shift (RWGS) or Methyl Formate 43
1.6.6 Domino Reactions with Ru Catalysts 44
References 46
1.7 Palladium-Catalyzed Hydroformylation 48
1.7.1 General Aspects 48
1.7.2 Mechanistic Investigations, Complexes, and Ligands 48
1.7.3 Some Applications 50
References 51
1.8 Platinum-Catalyzed Hydroformylation 52
1.8.1 General Aspects 52
1.8.2 Mechanistic Investigations, Complexes, and Ligands 53
1.8.3 Some Applications 57
References 60
1.9 Iridium-Catalyzed Hydroformylation 62
1.9.1 General Aspects 62
1.9.2 Mechanistic Investigations, Complexes, and Ligands 62
1.9.3 Some Applications 65
References 66
1.10 Iron-Catalyzed Hydroformylation 67
1.10.1 General Aspects 67
1.10.2 Monometallic Iron Catalysts 67
1.10.3 Iron Complexes as Additives to Conventional Hydroformylation Catalysts 69
References 70
2 Organic Ligands 73
References 77
2.1 Phosphines - Typical Structures and Individuals, Syntheses, and Selected Properties 78
2.1.1 Monodentate Phosphines 78
2.1.2 Diphosphines 86
2.1.3 Triphosphines 91
2.1.4 Tetraphosphines 93
2.1.5 Ligands for Special Applications 95
2.1.5.1 Phosphines with Improved Solubility in Aromatic Solvents 96
2.1.5.2 Phosphines-Bearing Functional Groups 97
2.1.5.3 Phosphines Designed for Hydroformylation in Ionic Liquids (ILs) 102
2.1.5.4 Dendrimers as Support for Phosphines 105
2.1.5.5 Polymer-Supported Phosphines 114
2.1.6 Decomposition of Phosphines 118
2.1.6.1 Enemies of Phosphines in the Absence of the Metal 120
2.1.6.2 Decomposition of Phosphines in the Presence of Metals 122
References 128
2.2 Phosphites - Synthesis, Typical Examples, and Degradation 136
2.2.1 General Aspects 136
2.2.2 Synthesis of Alcohols 138
2.2.2.1 Mono-, Bi-, and Polyphenols 138
2.2.2.2 Benzylic Alcohols 145
2.2.2.3 Aliphatic Diols 146
2.2.3 Synthesis of Phosphites - Typical Routes and Problems 150
2.2.4 Types and Selected Ligands 158
2.2.4.1 Mono-, Di-, and Triphosphites 158
2.2.4.2 Polyphosphites Linked to Supports 162
2.2.5 Stereochemical Considerations 162
2.2.6 Structure-Activity Relationships in Hydroformylation 166
2.2.7 Rhodium Phosphite Precatalysts 167
2.2.8 Degradation Pathways of Phosphites 169
2.2.8.1 Reaction with Oxygen and Peroxides 169
2.2.8.2 Reaction with Water 170
2.2.8.3 Reaction with Alcohols 176
2.2.8.4 Degradation with Acids 176
2.2.8.5 Degradation and Consequences for Rhodium Complex Formation 178
2.2.8.6 Measures against Degradation 179
References 182
2.3 Phosphoramidites - Syntheses, Selected Structures, and Degradation 189
2.3.1 Introduction 189
2.3.2 Use of Phosphoramidites in Rh-Catalyzed Hydroformylation 191
2.3.2.1 Non-Asymmetric Hydroformylation 191
2.3.2.2 Asymmetric Hydroformylation with Phosphoramidites Ligands 196
2.3.3 Stability of Phosphoramidites 200
2.3.3.1 General Aspects 200
2.3.3.2 Measures against Deterioration 205
2.3.4 Conclusions 208
References 209
2.4 Chiral Phosphorus Ligands for Stereoselective Hydroformylation 211
2.4.1 General Remarks 211
2.4.2 Synthesis of Chiral Ligands 212
2.4.2.1 Privileged Ligands 212
2.4.2.2 Chiral Ligands for Special Substrates 224
2.4.3 Comparison of the Catalytic Performance of Some Privileged Ligands 227
2.4.4 Conclusions 228
References 229
2.5 N-Heterocyclic Carbenes (NHCs) as Ligands in Transition-Metal-Catalyzed Hydroformylation 232
2.5.1 Introduction 232
2.5.2 Electronic and Steric Features of NHCs 233
2.5.3 Historical Aspects 235
2.5.4 Typical Structures of Azolium Salts and NHCs Used as Ligands 236
2.5.5 Synthesis of Carbene Ligands and Their Metal Complexes 236
2.5.5.1 Synthesis of Imidazolium Salts 236
2.5.5.2 Synthesis of NHCs 238
2.5.5.3 Synthesis of NHC-Metal Complexes 239
2.5.6 Conclusions 263
References 263
3 Syngas and Alternative Syngas Sources 267
3.1 General Remarks 267
3.2 Generation of Syngas from Formaldehyde or Paraformaldehyde 269
3.3 Syngas Generation from CO 2 273
3.4 Syngas Generation from Methanol 277
3.5 Formic Acid or Methyl Formate as Source for Hydrogen 278
3.6 Alcohols from Biomass as Source of Syngas 280
3.7 Conclusions 282
References 282
Volume 2
4 Hydroformylation Reactions 285
5 Tandem and Other Sequential Reactions Using a Hydroformylation Step 379
6 Synthesis of Special Products via Hydroformylation 525
7 Hydroformylation in Nonconventional Reaction Media 627
8 Decarbonylation and Dehydrocarbonylation of Aldehydes 665
9 Selected Aspects of Production Processes 677
Index 693
