Rhodium Catalyzed Hydroformylation

Front Matter......Page 1
Preface......Page 5
Table of Contents......Page 0
Table of Contents......Page 7
1.1 History of Phosphorus Ligand Effects......Page 12
1.2 Hydroformylation......Page 17
1.3 Ligand Parameters......Page 19
2.1 Introduction......Page 25
2.2 Regioselectivity in the Rhodium-Catalyzed Hydroformylation of Vinyl and Vinylidenic Substrates......Page 26
2.2.2 Influence of the Alkene Structure on the Regioselectivity......Page 27
2.2.3 Influence of Temperature......Page 31
2.3 Mechanism of the Hydroformylation of Vinyl and Vinylidenic Alkenes......Page 32
2.3.2 Behavior of the Isomeric Alkyl-Metal Intermediates via Deuterioformylation......Page 34
2.3.3 In Situ IR Investigation of the Formation and Reactivity of Acylrhodium Intermediates......Page 38
2.4.1 Influence of the Nature of the Substrate......Page 39
2.4.2 Influence of the Reaction Parameters......Page 41
3.1 Introduction......Page 44
3.2.1 Catalysis......Page 46
3.2.2 Mechanistic and Kinetic Studies......Page 49
3.3.1 Catalysis......Page 53
3.3.2 Mechanistic and Kinetic Studies......Page 57
3.4.1 Hydroformylation of Less Reactive Internal and Functionalized Alkenes......Page 64
3.4.2 Formation of Linear Aldehydes Starting from Internal Alkenes......Page 66
3.5 Calixarene Based Phosphites......Page 68
4.1.1 Introduction......Page 72
4.1.2 The Mechanism......Page 73
4.1.3 Ligand Effects......Page 75
4.1.4 In Situ Studies......Page 77
4.1.5 Kinetics......Page 78
4.1.6 Regioselectivity......Page 81
4.1.7 Conclusion......Page 84
4.2.1 Introduction......Page 85
4.2.2 Ferrocene Based Diphosphine Ligands......Page 87
4.2.3 BISBI Ligands and the Natural Bite Angle......Page 91
4.2.4 Xantphos Ligands: Tunable Bite Angles......Page 96
4.2.5 The Mechanism, Regioselectivity, and the Bite Angle. Concluding Remarks......Page 105
5.1 Introduction......Page 115
5.2.1 C2 Symmetric Chiral Diphosphite Ligands......Page 117
5.2.2 Catalyst Preparation and Hydroformylation......Page 119
5.2.3 Characterisation of [RhH(L)(CO2) ] Intermediates. Solution Structures of Hydroformylation Catalysts......Page 121
5.2.4 Structure versus Stability and Enantioselectivity......Page 123
5.2.5 Chiral Cooperativity and Effect of Substituents in Diastereomeric Diphosphite Ligands......Page 124
5.2.6 C1 Sugar Backbone Derivatives. Diphosphinite and Diphosphite Ligands......Page 129
5.3.2 Rhodium Complexes with BINAPHOS and Related Ligands......Page 132
5.3.3 [RhH(CO)2(BINAPHOS)] Complexes; Models For Enantioselectivity......Page 135
5.3.5 Chiral Phosphine-Phosphite Ligands Containing a Stereocenter in the Backbone......Page 137
5.4.2 C1 Diphosphines as Chiral Ligands......Page 139
5.4.3 C2 Diphosphines as Chiral Ligands......Page 140
5.4.4 The Rh/BDPP System. HPNMR and HPIR Studies under Hydroformylation Conditions......Page 144
5.5.1 Regioselectivity......Page 146
5.5.2 Enantioselectivity and Conclusions......Page 148
6.1 Introduction......Page 153
6.2 Hydro Formylation of Unfunctionalized Alkenes......Page 154
6.3 Hydroformylation of Functionalized Alkenes......Page 157
6.4 Substrate Directed Stereoselectivity......Page 163
6.5 Control of the Regio- and Stereoselectivity by Heteroatomdirected Hydroformylation......Page 168
6.6 Consecutive Processes under Hydroformylation Conditions......Page 172
6.6.1 Hydroformylation-Acetalization (Intramolecular)......Page 173
6.6.2 Hydroformylation-Acetalization (Intermolecular)......Page 174
6.6.3 Hydroformylation-Amination (Intramolecular)......Page 176
6.6.4 Hydroformylation-Amination-Reduction. Hydroaminomethylation......Page 180
6.6.5 Consecutive hydroformylation-aldol reaction......Page 183
6.6.6 Consecutive Hydroformylation-Wittig Reaction......Page 185
6.7 Alkyne Hydroformylation......Page 186
6.8 Concluding Remarks......Page 190
7.1.1 Why Two-Phase Catalysis? Scope and Limitations......Page 196
7.1.2 Concepts for Two-Phase Hydroformylation......Page 197
7.2.2 Ligand Developments......Page 198
7.2.3 Kinetics and Catalyst Pre-Formation......Page 200
7.2.4 Process Description......Page 203
7.2.5 Status of the Operated Plants......Page 204
7.2.6 Economics......Page 205
7.3.1 Ethylene to Propanal: Why Not Applied?......Page 206
7.3.2 Long-Chain Alkenes......Page 207
8.1 Introduction......Page 210
8.2 Economics......Page 211
8.3.1 Catalyst Selectivity......Page 213
8.3.2 Catalyst Activity......Page 214
8.4.1 Rhodium Loss Routes......Page 215
8.4.2 Ligand Loss Routes......Page 216
8.4.3 Catalyst Recovery Processes......Page 217
8.5 Process Concepts......Page 218
8.5.1 Type I: Stripping Reactor Process/Rh Containment in Reactor......Page 219
8.5.2 Type II: Liquid Recycle Process/Use of Distillative Separation......Page 220
8.5.3 Type III: Two-Phase Reaction/Extraction Process......Page 222
8.5.4 Type IV: Extraction after One-Phase Reaction......Page 223
8.6.1 Hydroformylation of Butenes......Page 227
8.6.3 Linear Higher Alkenes to Mainly Detergent Alcohols......Page 230
8.6.4 1,4-Butanediol......Page 232
8.6.5 Nylon Monomers......Page 233
9.2 Catalyst Preparation......Page 239
9.3.2 Oxidation of Phosphorus Ligands......Page 241
9.3.3 Phosphorus-Carbon Bond Breaking in Phosphines......Page 243
9.3.4 Decomposition of Phosphites......Page 249
9.3.5 Formation of Dormant Sites......Page 253
9.4 Concluding Remarks......Page 255
10.2 New Bimetallic Catalysts......Page 258
10.3.1 Micellar Catalysis......Page 261
10.3.2 Supported Aqueous Phase Catalysis (SAPC)......Page 265
10.3.3 Hydroformylation in Supercritical Fluids......Page 267
10.3.4 Fluorous Biphase Catalysis......Page 270
10.3.5 Dendrimer Supported Catalysts......Page 272
10.3.6 Novel Developments in Polymer Supported Catalyst......Page 274
10.4 Supramolecular Catalysis......Page 279
10.5 Conclusions......Page 282
C......Page 285
E......Page 286
K......Page 287
O......Page 288
S......Page 289
V......Page 290
X......Page 291