Home Shop Service Jobs Newsletter Company Sitemap Entertainment Shopping cart Deutsch
Books | Chemistry | Organic Chemistry | The Handbook of Homogeneous Hydrogenation | Table of contents
Browse our products
Books
 
Just published
Title search
Featured sites
Entertainment
Journals
Electronic Media
Choose your area of interest
 
  Contents  
 
 Foreword XIX
 Preface XXIII
 List of Contributors XXV
Part I Introduction, Organometallic Aspects and Mechanism of Homogeneous Hydrogenation  
1 Rhodium
Luis A. Oro and Daniel Carmona 		3
1.1 Introduction 3
1.1.1 Monohydride Hydrogenation Catalysts 4
1.1.2 Dihydride Hydrogenation Catalysts 4
1.2 The Early Years (19391970) 5
1.3 The [RhH(CO)(PPh3)3] Catalyst 6
1.4 The [RhCl(PPh3)3] Complex and Related Catalysts 8
1.5 The Cationic[Rh(diene)(PR3)X]+ Catalysts 11
1.6 Enantioselective Rhodium Catalysts 14
1.6.1 Hydrogenation of Alkenes 14
1.6.2 Hydrogenation of Ketones 19
1.6.3 Hydrogenation of Imines 20
1.6.4 Mechanism of Rhodium-Catalyzed Enantioselective Hydrogenation 21
1.7 Some Dinuclear Catalyst Precursors 26
1.8 Concluding Remark 26
Abbreviations 26
References 27
2 Iridium
Robert H. Crabtree 		31
2.1 Introduction 31
2.2 Historical Aspects 31
2.3 Organometallic Aspects 36
2.4 Catalysis 39
2.4.1 Enantioselective Versions of the Iridium Catalyst 39
2.4.2 Mechanism 40
2.4.3 Practical Considerations 42
Acknowledgments 43
Abbreviations 43
References 43
3 Ruthenium and Osmium
Robert H. Morris 		45
3.1 Introduction 45
3.2 Ruthenium 46
3.2.1 The First Catalysts for Alkene Hydrogenation: Mechanistic Considerations 46
3.2.2 Synthesis of Ruthenium Precatalysts and Catalysts 50
3.2.3 Dihydrogen Complexes and Non-Classical Hydrogen Bonding in Catalysis 52
3.2.4 Toward the Reduction of Simple Ketones, Nitriles, Esters and Aromatics with Monodentate Phosphine Systems 55
3.2.5 Enantiomeric Hydrogenation of Alkenes with Bidentate Ligand Systems 58
3.2.6 Enantiomeric Hydrogenation of Carbonyl Compounds 60
3.3 Osmium 64
Acknowledgment 66
Abbreviations 67
References 67
4 Palladium and Platinum
Paolo Pelagatti 		71
4.1 Introduction 71
4.2 Palladium 72
4.2.1 Phosphorus-Containing Catalysts 72
4.2.2 Nitrogen-Containing Catalysts 76
4.2.3 Other Catalysts 78
4.2.4 Mechanistic Aspects 79
4.3 Platinum 84
4.3.1 Platinum Complexes Activated with Sn(II) Salts 84
4.3.1.1 Phosphorus-Containing Catalysts 84
4.3.1.2 Other Catalysts 85
4.3.2 Platinum Complexes not Activated with Sn(II) Salts 86
4.3.3 Mechanistic Aspects 87
Abbreviations 89
References 89
5 Nickel
Elisabeth Bouwman 		93
5.1 Introduction 93
5.2 Coordination Chemistry and Organometallic Aspects of Nickel 94
5.2.1 Nickel--Hydride Complexes 94
5.2.2 Nickel-Alkene and Nickel-Alkyl Complexes 96
5.2.3 Mechanistic Aspects of Hydrogen Activation 97
5.3 Hydrogenation Catalysis 98
5.3.1 Ziegler Systems 98
5.3.2 Nickel Complexes of Oxygen- or Nitrogen-Containing Ligands 99
5.3.3 Nickel Complexes of Triphenylphosphane 100
5.3.4 Nickel Complexes of Didentate Phosphane Ligands 101
5.4 Concluding Remarks 107
Abbreviations 108
References 108
6 Hydrogenation with Early Transition Metal, Lanthanide and Actinide Complexes
Christophe Copéret 		111
6.1 Introduction 111
6.2 Mechanistic Considerations 112
6.3 Group IV Metal Hydrogenation Catalysts 113
6.3.1 Hydrogenation of Alkenes 113
6.3.2 Hydrogenation of Alkynes and Dienes 114
6.3.3 Enantioselective Hydrogenation of Alkenes 116
6.3.4 Enantioselective Hydrogenation of Imines and Enanimes 118
6.4 Hydrogenation Catalysts Based on Group III, Lanthanide, and Actinide Complexes 126
6.4.1 Hydrogenation of Alkenes with Group III Metal and Lanthanide Complexes 126
6.4.2 Hydrogenation of Dienes and Alkynes with Group III and Lanthanide Complexes 129
6.4.3 Hydrogenation of Imines with Group III and Lanthanide Complexes 131
6.4.4 Hydrogenation of Alkenes with Actinide Complexes 132
6.4.5 Enantiomeric Hydrogenation of Alkenes 134
6.5 Hydrogenation Catalysts Based on Groups VVII Transition-Metal Complexes 136
6.5.1 Hydrogenation of Alkenes and Dienes with Groups VVII Transition-Metal Complexes 136
6.5.2 Hydrogenation of Aromatics with Well-Defined Nb and Ta Aryloxide Complexes 138
6.6 Supported Early Transition-Metal Complexes as Heterogeneous Hydrogenation Catalysts 140
6.6.1 Supported Homogeneous Catalysts 140
6.6.2 Heterogeneous Catalysts Prepared via Surface Organometallic Chemistry 142
6.7 Conclusions 145
Acknowledgments 146
Abbreviations 146
References 146
7 Ionic Hydrogenations
R. Morris Bullock 		153
7.1 Introduction 153
7.2 Stoichiometric Ionic Hydrogenations 154
7.2.1 Stoichiometric Ionic Hydrogenations using CF3CO2H and HSiEt3 154
7.2.2 Stoichiometric Ionic Hydrogenations using Transition-Metal Hydrides 157
7.2.2.1 General Aspects 157
7.2.2.2 Transition-Metal Hydrides as Proton Donors 157
7.2.3 Transition Metal Hydrides as Hydride Donors 159
7.2.4 Stoichiometric Ionic Hydrogenation of Alkenes with Metal Hydrides as the Hydride Donor 164
7.2.5 Stoichiometric Ionic Hydrogenation of Alkynes 166
7.2.6 Stoichiometric Ionic Hydrogenation of Ketones and Aldehydes using Metal Hydrides as Hydride Donors and Added Acids as the Proton Donor 167
7.2.7 Stoichiometric Ionic Hydrogenation of Acyl Chlorides to Aldehydes with HOTf/Metal Hydrides 171
7.2.8 Stoichiometric Ionic Hydrogenation of Ketones with Metal Dihydrides 173
7.3 Catalytic Ionic Hydrogenation 174
7.3.1 Catalytic Ionic Hydrogenation of C=C Bonds 174
7.3.2 Catalytic Ionic Hydrogenation of Ketones by Anionic Cr, Mo, and W Complexes 174
7.3.3 Catalytic Ionic Hydrogenation of Ketones by Molybdenocene Complexes 176
7.3.4 Catalytic Ionic Hydrogenation of Ketones by Cationic Mo and W Complexes 178
7.3.4.1 In Solution 178
7.3.4.2 Solvent-free 181
7.3.4.3 N-Heterocyclic Carbene Complexes 182
7.3.5 Use of a Pd Hydride in Hydrogenation of C=C Bonds 184
7.3.6 Catalytic Hydrogenation of Iminium Cations by Ru Complexes 184
7.4 Ruthenium Complexes Having an OH Proton Donor and a RuH as Hydride Donor 186
7.4.1 The Shvo System 186
7.4.2 Hydrogenation of Imines by Shvo Complexes 189
7.4.3 Dehydrogenation of Imines and Alcohols by Shvo Complexes 191
7.4.4 Catalytic Hydrogenations with Metal--Ligand Bifunctional Catalysis 193
7.5 Catalytic Hydrogenation of Ketones by Strong Bases 193
7.6 Conclusion 194
Acknowledgments 194
Abbreviations 195
References 195
8 Homogeneous Hydrogenation by Defined Metal Clusters
Roberto A. Sánchez-Delgado 		199
8.1 Introduction 199
8.1.1 Is a Cluster the Real Catalyst? Fragmentation and Aggregation Phenomena 200
8.2 Hydrogenation of C=C Bonds 201
8.3 Hydrogenation of CC Bonds 206
8.4 Hydrogenation of Other Substrates 211
8.5 Concluding Remarks 212
Abbreviations 213
References 213
9 Homogeneous Hydrogenation: Colloids -- Hydrogenation with Noble Metal Nanoparticles
Alain Roucoux and Karine Philippot 		217
9.1 Introduction 217
9.2 Concepts 217
9.2.1 Electrostatic Stabilization 218
9.2.2 Steric Stabilization 219
9.3 Hydrogenation of Compounds with C=C Bonds 220
9.3.1 Use of Polymers as Stabilizers 220
9.3.2 Use of Non-Usual Polymers as Stabilizers 221
9.3.3 Use of Dendrimers as Stabilizers 225
9.3.4 Use of Surfactants as Stabilizers 226
9.3.5 Use of Polyoxoanions as Stabilizers 227
9.3.6 Use of Ligands as Stabilizers 228
9.3.7 Biomaterial as a Protective Matrix 232
9.3.8 Ionic Liquids used as Templates for the Stabilization of Metal Nanoparticles 233
9.3.9 Supercritical Microemulsions Used as Templates for the Stabilization of Metal Nanoparticles 236
9.3.10 Conclusion 238
9.4 Hydrogenation of Compounds with CC Bonds 238
9.5 Arene Hydrogenation 241
9.6 Hydrogenation of Compounds with C=O Bonds 245
9.7 Enantioselective Hydrogenation 249
9.8 Conclusion 252
Abbreviations 252
References 253
10 Kinetics of Homogeneous Hydrogenations: Measurement and Interpretation
Hans-Joachim Drexler, Angelika Preetz, Thomas Schmidt, and Detlef Heller 		257
10.1 Introduction 257
10.2 The Basics of Michaelis-Menten Kinetics 259
10.3 Hydrogenation From a Kinetic Viewpoint 263
10.3.1 Measurement of Concentration--Time Data and Possible Problems 263
10.3.1.1 Monitoring of Hydrogenations via Hydrogen Consumption 264
10.3.1.2 Monitoring of Hydrogenations by NMR and UV/Visible Spectroscopy 272
10.3.2 Gross-Kinetic Measurements 277
10.3.2.1 Derivation of Michaelis-Menten Kinetics with Various Catalyst-Substrate Complexes 277
10.3.2.2 Data from Gross Kinetic Measurements 280
Abbreviations 288
References 288
Part II Spectroscopic Methods in Homogeneous Hydrogenation  
11 Nuclear Magnetic Resonance Spectroscopy in Homogeneous Hydrogenation Research
N. Koen de Vries 		297
11.1 Introduction 297
11.1.1 Nuclear Magnetic Resonance (NMR) 297
11.1.2 NMR in Homogeneous Hydrogenation Research 298
11.2 NMR Methods 299
11.2.1 General 299
11.2.2 Chemical Shift 300
11.2.2.1 General 300
11.2.2.2 Chemical Shifts in Homogeneous Hydrogenation Research 300
11.2.3 Coupling Constant 301
11.2.4 2D-NMR 302
11.2.4.1 General 302
11.2.4.2 2D-NMR in Homogeneous Hydrogenation Research 302
11.2.5 Variable Temperature and Variable Pressure Studies 307
11.2.5.1 General 307
11.2.5.2 Variable-Temperature Studies in Homogeneous Hydrogenation Research 307
11.2.5.3 Variable-Pressure Studies in Homogeneous Hydrogenation Research 308
11.2.6 PGSE NMR Diffusion Methods 309
11.3 Outlook 309
Abbreviations 310
References 310
12 Parahydrogen-Induced Polarization: Applications to Detect Intermediates of Catalytic Hydrogenations
Joachim Bargon 		313
12.1 In-Situ Spectroscopy 313
12.1.1 In-Situ NMR Spectroscopy 313
12.1.2 In-Situ PHIP-NMR Spectroscopy 314
12.2 Ortho- and Parahydrogen 315
12.2.1 Magnetic Field Dependence of the PHIP-Phenomenon: PASADENA and ALTADENA Conditions 316
12.2.2 PHIP, CIDNP, and Radical Mechanisms 318
12.2.3 Preparation of Parahydrogen 319
12.2.3.1 Parahydrogen Enrichment 319
12.2.3.2 High-Pressure Apparatus for Parahydrogen Enrichment 320
12.2.3.3 Enrichment of Parahydrogen using Closed-Circuit Cryorefrigeration 321
12.2.4 Preparation of Orthohydrogen 322
12.2.5 Thermal Conductivity Cells for Ortho/Para Determination 322
12.2.6 Determination of the Ortho/Para Ratio 323
12.2.7 Enrichment of Ortho- or Paradeuterium 323
12.3 Applications of PHIP-NMR Spectroscopy 324
12.3.1 In-Situ PHIP-NMR Spectroscopy of Homogeneous Hydrogenations 324
12.3.1.1 Activation of Dihydrogen 324
12.3.1.2 Concepts of Reaction Mechanisms 324
12.3.2 In-Situ PHIP-NMR Observation of Mono- and Binuclear Rhodium Dihydride Complexes 325
12.3.2.1 Reactions of [RhCl(NBD)]2 with Parahydrogen in the Presence of Tertiary Phosphines 325
12.3.2.2 Formation of the Binuclear Complexes [(H)(Cl)Rh(PMe3)2(-Cl)( -H)Rh(PMe3)] and [(H)(Cl)Rh(PMe2Ph)2(-Cl)( -H)Rh(PMe2Ph)] 328
12.3.2.3 General Procedure for the Generation of the Complexes [Rh(H)2ClL3] (L=Phosphine) 329
12.3.3.3 Intermediate Dihydrides of Cationic Rh Catalysts 329
12.3.3.4 Obtaining Structural Information using 13C-Labeled Substrates 332
12.4 Catalyst-Attached Products as Observable Intermediates 335
12.4.1 Enantioselective Substrates 336
12.4.2 Chiral Catalysts 336
12.4.3 Determination of Kinetic Constants 338
12.4.4 Computer-Assisted Prediction and Analysis of the Polarization Patterns: DYPAS2 341
12.5 Colloidal Catalysts 342
12.5.1 In-Situ PHIP-NMR Investigation of the Hydrogenation of Ethynylbenzene by Pdx[N(octyl) 4Cl] y 342
12.6 Transfer of Proton Polarization to Heteronuclei 344
12.6.1 General Aspects 344
12.6.2 Polarization Transfer to 13C 346
12.6.3 Polarization Transfer to 19F 352
12.6.4 Parahydrogen-Assisted Signal Enhancement for Magnetic Resonance Imaging 353
12.7 Catalysts Containing other Transition Metals 354
12.8 Summary and Conclusions 354
Acknowledgment 355
Abbreviations 355
References 356
13 A Tour Guide to Mass Spectrometric Studies of Hydrogenation Mechanisms
Corbin K. Ralph, Robin J. Hamilton, and Steven H. Bergens 		359
13.1 Introduction 359
13.2 A General Description of ESI-MS 360
13.3 Mechanistic Hydrogenation Studies 364
13.4 Conclusions 369
Acknowledgments 370
Abbreviations 370
References 370
Part III Homogeneous Hydrogenation by Functional Groups  
14 Homogeneous Hydrogenation of Alkynes and Dienes
Alexander M. Kluwer and Cornelis J. Elsevier 		375
14.1 Stereoselective Homogeneous Hydrogenation of Alkynes to Alkenes 375
14.1.1 Introduction 375
14.1.2 Chromium Catalysts 376
14.1.3 Iron Catalysts 377
14.1.4 Ruthenium Catalysts 378
14.1.5 Osmium Catalysts 382
14.1.6 Rhodium Catalysts 384
14.1.7 Iridium Catalysts 386
14.1.8 Palladium Catalysts 388
14.1.9 Conclusions 394
14.2 Homogeneous Hydrogenation of Dienes to Monoenes 394
14.2.1 Introduction 394
14.2.2 Zirconium Catalysts 395
14.2.3 Chromium Catalysts 397
14.2.4 Ruthenium Catalysts 400
14.2.5 Cobalt Catalysts 402
14.2.6 Rhodium Catalysts 402
14.2.7 Palladium and Platinum Catalysts 406
14.2.8 Conclusions 408
Abbreviations 409
References 409
15 Homogeneous Hydrogenation of Aldehydes, Ketones, Imines and Carboxylic Acid Derivatives: Chemoselectivity and Catalytic Activity
Matthew L. Clarke and Geoffrey J. Roff 		413
15.1 Introduction 413
15.2 Hydrogenation of Aldehydes 414
15.2.1 Iridium Catalysts 414
15.2.2 Rhodium Catalysts 417
15.2.2.1 Rh-amine Catalysts 417
15.2.2.2 Cationic Rhodium Phosphine Catalysts 418
15.2.2.3 Water-Soluble Rh Catalysts 419
15.2.3 Ruthenium Catalysts 420
15.2.3.1 Ru-PPh3 Catalysts 420
15.2.3.2 Polydentate Ru Catalysts 421
15.2.3.3 Diamine-Modified Ru Catalysts 422
15.2.3.4 Ru-TPPMS/TPPTS Catalysts 423
15.2.4 Other Metal Catalysts 425
15.2.4.1 Copper 425
15.2.4.2 Osmium 425
15.3 Hydrogenation of Ketones 426
15.3.1 Iridium Catalysts 426
15.3.2 Rhodium Catalysts 428
15.3.2.1 Rh-Phosphine Catalysts 428
15.3.2.2 Water-Soluble Rh Catalysts 430
15.3.3 Ruthenium Catalysts 431
15.3.3.1 Ruthenium Carbonyl Clusters 431
15.3.3.2 Ru--PPh3 Complexes 431
15.3.3.3 Diamine-Modified Ru Catalysts 433
15.3.3.4 Other Ru Catalysts 434
15.3.4 Other Metal Catalysts 435
15.3.4.1 Copper 435
15.3.4.2 Metal Carbonyls 436
15.4 Domino-Hydroformylation-Reduction Reactions 436
15.4.1 Cobalt Catalysts 436
15.4.2 Rhodium Catalysts 437
15.5 Reductive Amination of Ketones and Aldehydes 437
15.6 Hydroaminomethylation of Alkenes (Domino Hydroformylation-Reductive Amination) 439
15.7 Hydrogenation of Carboxylic Acid Derivatives 441
15.7.1 Hydrogenation of Acids and Anhydrides 442
15.7.2 Hydrogenation of Esters 445
15.8 Summary and Outlook 450
Abbreviations 451
References 452
16 Hydrogenation of Arenes and Heteroaromatics
Claudio Bianchini, Andrea Meli, and Francesco Vizza 		455
16.1 Introduction 455
16.2 Hydrogenation of Arenes 456
16.2.1 Molecular Catalysts in Different Phase-Variation Systems 456
16.2.2 Molecular Catalysts Immobilized on Support Materials 466
16.3 Hydrogenation of Heteroaromatics 470
16.3.1 Molecular Catalysts in Different Phase-Variation Systems 470
16.3.1.1 S-Heteroaromatics 470
16.3.1.2 N-Heteroaromatics 474
16.3.1.3 O-Heteroaromatics 479
16.3.2 Molecular Catalysts Immobilized on Support Materials 479
16.4 Stereoselective Hydrogenation of Prochiral Heteroaromatics 481
16.4.1 Molecular Catalysts in Homogeneous Phase 481
16.4.2 Molecular Catalysts Immobilized on Support Materials 484
Abbreviations 484
References 485
17 Homogeneous Hydrogenation of Carbon Dioxide
Philip G. Jessop 		489
17.1 Introduction 489
17.2 Reduction to Formic Acid 490
17.2.1 Insertion Mechanisms 494
17.2.2 Ionic Hydrogenation 497
17.2.3 Concerted Ionic Hydrogenation 498
17.2.4 Bicarbonate Hydrogenation 498
17.2.5 Other Mechanisms 499
17.3 Reduction to Oxalic Acid 499
17.4 Reduction to Formate Esters 500
17.4.1 In the Presence of Alcohols 500
17.4.2 In the Presence of Alkyl Halides 502
17.4.3 In the Presence of Epoxides 503
17.5 Reduction to Formamides 504
17.6 Reduction to Other Products 506
17.7 Concluding Remarks 507
Acknowledgments 507
Abbreviations 508
References 508
18 Dehalogenation Reactions
Attila Sisak and Ottó Balzás Simon 		513
18.1 Introduction 513
18.2 Catalytic Dehalogenation with Various Reducing Agents 517
18.2.1 Molecular Hydrogen 517
18.2.2 Simple and Complex Metal Hydrides 520
18.2.3 Hydrosilanes and Hydrostannanes 524
18.2.4 Hydrogen Donors other than Hydrides 526
18.2.5 Biomimetic Dehalogenations 528
18.2.6 Electrochemical Reductions 532
18.2.7 Miscellaneous Reducing Methods 533
18.3 Mechanistic Considerations 534
18.3.1 Activation of the CX Bond 535
18.3.1.1 Oxidative Addition 535
18.3.1.2 -Bond Metathesis 537
18.3.1.3 SN2 Attack of the Hydride Ligand 538
18.3.1.4 1,2-Insertion 538
18.3.2 Reaction Steps Involving the Reducing Agents 538
18.3.3 Formation of the Product 539
18.4 Concluding Remarks 540
Acknowledgments 540
Abbreviations 540
References 541
19 Homogeneous Catalytic Hydrogenation of Polymers
Garry L. Rempel, Qinmin Pan, and Jialong Wu 		547
19.1 General Introduction 547
19.1.1 Diene-Based Polymers 547
19.1.2 Hydrogenation of Diene-Based Polymers 548
19.1.2.1 Heterogeneous Catalysts 549
19.1.2.2 Homogeneous Catalysts 550
19.2 Reaction Art 551
19.2.1 Catalyst Techniques 551
19.2.2 Hydrogenation Kinetic Mechanism 565
19.2.2.1 Rhodium-Based Catalysts 565
19.2.2.2 Ruthenium-Based Catalysts 568
19.2.2.3 Osmium-Based Catalysts 571
19.2.2.4 Palladium Complexes 572
19.2.3 Kinetic Mechanism Discrimination 573
19.3 Engineering Art 573
19.3.1 Catalyst Recovery 574
19.3.1.1 Precipitation 575
19.3.1.2 Adsorption 575
19.3.2 Solvent Recycling 576
19.3.3 Reactor Technology and Catalytic Engineering Aspects 577
19.4 A Commercial Example: Production of HNBR via a Homogeneous Hydrogenation Route 578
19.5 Future Outlook and Perspectives 579
Abbreviations 579
References 579
20 Transfer Hydrogenation Including the Meerwein-Ponndorf-Verley Reduction
Dirk Klomp, Ulf Hanefeld, and Joop A. Peters 		585
20.1 Introduction 585
20.2 Reaction Mechanisms 587
20.2.1 Hydrogen Transfer Reduction of Carbonyl Compounds 588
20.2.1.1 Meerwein-Ponndorf-Verley Reduction and Oppenauer Oxidation 588
20.2.1.2 Transition Metal-Catalyzed Reductions 590
20.2.2 Transfer Hydrogenation Catalysts for Reduction of C--C Double and Triple Bonds 595
20.3 Reaction Conditions 597
20.3.1 Hydrogen Donors 597
20.3.2 Solvents 600
20.3.3 Catalysts and Substrates 601
20.3.4 Selectivity 603
20.4 Related Reactions and Side-Reactions 609
20.4.1 Aldol Reaction 609
20.4.2 Tishchenko Reaction 609
20.4.3 Cannizzaro Reaction 609
20.4.4 Decarbonylation 610
20.4.5 Leuckart-Wallach and Eschweiler-Clarke Reactions 610
20.4.6 Reductive Acetylation of Ketones 610
20.4.7 Other Hydrogen Transfer Reactions 611
20.5 Racemizations 612
Abbreviations 627
References 627
21 Diastereoselective Hydrogenation
Takamichi Yamagishi 		631
21.1 Introduction 631
21.2 Hydrogenation of Alkenes, Ketones, and Imines 631
21.3 Substrate-Directive Diastereoselective Hydrogenation 638
21.3.1 Hydrogenation of Cyclic Alcohols with Endo- or Exo-Cyclic Olefinic Bond 638
21.3.2 Hydrogenation of Acyclic Allyl and Homoallyl Alcohols 653
21.3.3 Ester Unit- or Amide-Directive Hydrogenation 667
21.4 Hydrogenation of Dehydrooligopeptides 671
21.5 Diastereoselective Hydrogenation of Keto-Compounds 676
21.5.1 Substrate-Directive Hydrogenation of Keto-Compounds 681
21.5.2 Hydrogenation of Diketo Esters and Diketones 684
21.6 Kinetic Resolution to Selectively Afford Diastereomers and Enantiomers 691
21.7 Kinetic Resolution of Keto- and Imino-Compounds 694
21.8 Dynamic Kinetic Resolution 697
21.9 Conclusions 701
Abbreviations 708
References 708
22 Hydrogen-Mediated CarbonCarbon Bond Formation Catalyzed by Rhodium
Chang-Woo Cho and Michael J. Krische 		713
22.1 Introduction and Mechanistic Considerations 713
22.2 Reductive Coupling of Conjugated Enones and Aldehydes 716
22.2.1 Intramolecular Reductive Aldolization 716
22.2.2 Intermolecular Reductive Aldolization 720
22.3 Reductive Coupling of 1,3-Cyclohexadiene and -Ketoaldehydes 723
22.4 Reductive Coupling of Conjugated Enynes and Diynes with Activated Aldehydes and Imines 726
22.5 Reductive Cyclization of 1,6-Diynes and 1,6-Enynes 733
22.6 Conclusion 736
Acknowledgments 737
Abbreviations 737
References 737
Part IV Asymmetric Homogeneous Hydrogenation  
23 Enantioselective Alkene Hydrogenation: Introduction and Historic Overview
David J. Ager 		745
23.1 Introduction 745
23.2 Development of CAMP and DIPAMP 746
23.3 DIOP 749
23.4 Ferrocene Ligands 753
23.4.1 Ferrocene Hybrids 756
23.5 Atropisomeric Systems 756
23.6 DuPhos 758
23.7 Variations at Phosphorus 760
23.8 Monophosphorus Ligands 762
23.9 A Return to Monodentate Ligands 762
23.10 Summary 763
References 764
24 Enantioselective Hydrogenation: Phospholane Ligands
Christopher J. Cobley and Paul H. Moran 		773
24.1 Introduction and Extent of Review 773
24.2 Phospholane Ligands: Synthesis and Scope 774
24.2.1 Early Discoveries and the Breakthrough with DuPhos and BPE 774
24.2.2 Modifications to the Backbone 778
24.2.3 Modifications to the Phospholane Substituents 779
24.2.4 Other Phospholane-Containing Ligands 783
24.2.5 Related Phosphacycle-Based Ligands 786
24.3 Enantioselective Hydrogenation of Alkenes 788
24.3.1 Enantioselective Hydrogenation of a-Dehydroamino Acid Derivatives 788
24.3.2 Enantioselective Hydrogenation of b-Dehydroamino Acid Derivatives 801
24.3.3 Enantioselective Hydrogenation of Enamides 806
24.3.4 Enantioselective Hydrogenation of Unsaturated Acid and Ester Derivatives 810
24.3.5 Enantioselective Hydrogenation of Unsaturated Alcohol Derivatives 816
24.3.6 Enantioselective Hydrogenation of Miscellaneous C=C Bonds 819
24.4 Enantioselective Hydrogenation of C=O and C=N Bonds 820
24.4.1 Enantioselective Hydrogenation of Ketones 820
24.4.2 Enantioselective Hydrogenation of Imines and C=NX Bonds 822
24.5 Concluding Remarks 823
Abbreviations 823
References 824
25 Enantioselective Hydrogenation of Alkenes with Ferrocene-Based Ligands
Hans-Ulrich Blaser, Matthias Lotz, and Felix Spindler 		833
25.1 Introduction 833
25.2 Ligands with Phosphine Substituents Bound to One Cyclopentadiene Ring 835
25.3 Ligands with Phosphine Substituents Bound to both Cyclopentadiene Rings 835
25.3.1 Bppfa, Ferrophos, and Mandyphos Ligands 836
25.3.2 Miscellaneous Diphosphines 837
25.4 Ligands with Phosphine Substituents Bound to a Cyclopentadiene Ring and to a Side Chain 839
25.4.1 Josiphos 839
25.4.2 Immobilized Josiphos and Josiphos Analogues 841
25.4.3 Taniaphos 842
25.4.3 Various Ligands 843
25.5 Ligands with Phosphine Substituents Bound only to Side Chains 844
25.6 Major Applications of Ferrocene Diphosphine-Based Catalysts 847
25.6.1 Hydrogenation of Substituted Alkenes 848
25.6.2 Hydrogenation of C=O and C=N Functions 848
Abbreviations 850
References 850
26 The other Bisphosphine Ligands for Enantioselective Alkene Hydrogenation
Yongxiang Chi, Wenjun Tang, and Xumu Zhang 		853
26.1 Introduction 853
26.2 Chiral Bisphosphine Ligands 853
26.2.1 Atropisomeric Biaryl Bisphosphine Ligands 853
26.2.2 Chiral Bisphosphine Ligands Based on DIOP Modifications 860
26.2.3 P-Chiral Bisphosphine Ligands 861
26.2.4 Other Bisphosphine Ligands 862
26.3 Applications in Enantioselective Hydrogenation of Alkenes 864
26.3.1 Enantioselective Hydrogenation of -Dehydroamino Acid Derivatives 864
26.3.2 Enantioselective Hydrogenation of Enamides 866
26.3.3 Enantioselective Hydrogenation of (-Acylamino) Acrylates 868
26.3.4 Enantioselective Hydrogenation of Enol Esters 870
26.3.5 Enantioselective Hydrogenation of Unsaturated Acids and Esters 872
26.3.5.1 ,-Unsaturated Carboxylic Acids 872
26.3.5.2 ,-Unsaturated Esters, Amides, Lactones, and Ketones 874
26.3.5.3 Itaconic Acids and Their Derivatives 874
26.3.6 Enantioselective Hydrogenation of Unsaturated Alcohols 875
26.4 Concluding Remarks 877
References 877
27 Bidentate Ligands Containing a HeteroatomPhosphorus Bond
Stanton H.L. Kok, Terry T.-L. Au-Yeung, Hong Yee Cheung, Wing Sze Lam, Shu Sun Chan, and Albert S.C. Chan 		883
27.1 Introduction 883
27.2 Aminophosphine-Phosphinites (AMPPs) 883
27.3 Bisphosphinamidite Ligands 907
27.4 Mixed Phosphine-Phosphoramidites and Phosphine-Aminophosphine Ligands 918
27.5 Bisphosphinite Ligands (One P--O Bond) 924
27.6 Bisphosphonite Ligands (Two P--O Bonds) 978
27.7 Bisphosphite Ligands (Three P--O Bonds) 980
27.8 Other Mixed-Donor Bidentate Ligands 981
27.9 Ligands Containing Neutral S-Donors 983
Acknowledgments 988
Abbreviations 988
References 988
28 Enantioselective Alkene Hydrogenation: Monodentate Ligands
Michel van den Berg, Ben L. Feringa, and Adriaan J. Minnaard 		995
28.1 Introduction 995
28.2 Monodentate Phosphines 997
28.3 Monodentate Phosphonites 1000
28.4 Monodentate Phosphites 1000
28.5 Monodentate Phosphoramidites 1005
28.6 Monodentate Phosphinites, Aminophosphinites, Diazaphospholidines and Secondary Phosphine Oxides 1010
28.7 Hydrogenation of N-Acyl--Dehydroamino Acids and Esters 1011
28.8 Hydrogenation of Unsaturated Acids and Esters 1014
28.9 Hydrogenation of N-Acyl Enamides, Enol Esters and Enol Carbamates 1016
28.10 Hydrogenation of N-Acyl--Dehydroamino Acid Esters 1020
28.11 Hydrogenation of Ketones and Imines 1021
28.12 Conclusions 1023
Abbreviations 1024
References 1024
29 P,N and Non-Phosphorus Ligands
Andreas Pfaltz and Sharon Bell 		1029
29.1 Introduction 1029
29.2 Oxazoline-Derived P,N Ligands 1030
29.2.1 Phosphino-oxazolines 1030
29.2.2 Phosphite and Phosphinite Oxazolines 1033
29.2.3 Oxazoline-Derived Ligands Containing a P--N Bond 1036
29.2.4 Structurally Related Ligands 1038
29.3 Pyridine and Quinoline-Derived P,N Ligands 1040
29.4 Carbenoid Imidazolylidene Ligands 1042
29.5 Metallocenes 1043
29.6 Other Ligands 1044
29.7 Conclusions 1046
Abbreviations 1046
References 1047
30 Enantioselective Hydrogenation of Unfunctionalized Alkenes
Andreas Pfaltz and Sharon Bell 		1049
30.1 Introduction 1049
30.2 Terminal Alkenes 1050
30.2.1 2-Aryl-1-Butenes 1050
30.2.2 Other Terminal Alkenes 1054
30.3 Trisubstituted Alkenes 1056
30.3.1 Introduction 1056
30.3.2 Ir Catalysts 1057
30.3.3 Standard Test Substrates 1057
30.3.4 Other Substrates 1063
30.4 Tetrasubstituted Alkenes 1066
30.4.1 Substrates 1066
30.5 Dienes and Trienes 1067
30.6 Conclusions 1069
Abbreviations 1070
References 1070
31 Mechanism of Enantioselective Hydrogenation
John M. Brown 		1073
31.1 Introduction 1073
31.2 Rhodium-Catalyzed Hydrogenations 1074
31.2.1 Background 1074
31.2.2 More Recent Developments 1076
31.2.3 Transient and Reactive Intermediates in Rhodium Enantioselective Hydrogenation 1078
31.2.4 Mnemonics for the Sense of Enantioselective Hydrogenation 1082
31.2.5 Status of the Computational Study of Rhodium-Complex-Catalyzed Enantioselective Hydrogenation 1082
31.2.6 Monophosphines in Rhodium-Complex-Catalyzed Enantioselective Hydrogenation 1086
31.2.7 Mechanism of Hydrogenation of b-Dehydroamino Acid Precursors 1087
31.2.8 Current Status of Rhodium Hydrogenations 1088
31.3 Ruthenium-Complex-Catalyzed Hydrogenations 1093
31.3.1 Reactive Intermediates in Ruthenium-Complex-Catalyzed Hydrogenations 1093
31.3.2 Kinetic Analysis of Ruthenium-Complex-Catalyzed Hydrogenations 1093
31.4 Iridium-Complex-Catalyzed Hydrogenations 1094
31.4.1 Background 1094
31.4.2 Mechanistic and Computational Studies 1095
31.4.3 Counter-Ion Effects 1097
31.5 Summary and Conclusions 1098
Acknowledgments 1099
Abbreviations 1099
References 1099
32 Enantioselective Ketone and b-Keto Ester Hydrogenations (Including Mechanisms)
Takeshi Ohkuma and Ryoji Noyori 		1105
32.1 Chiral Ligands 1105
32.2 -Keto Esters and Analogues 1107
32.2.1 -Keto Esters 1107
32.2.2 1,3-Diketones 1122
32.2.3 -Keto Phosphonates, Sulfonates, and Sulfones 1125
32.2.4 Dynamic Kinetic Resolution 1127
32.3 Simple Ketones 1131
32.3.1 Alkyl Aryl Ketones 1131
32.3.2 Hetero-Substituted Aromatic Ketones 1141
32.3.3 Diaryl Ketones 1144
32.3.4 Heteroaromatic Ketones 1144
32.3.5 Dialkyl Ketones 1147
32.3.6 Unsaturated Ketones 1148
32.3.7 Kinetic Resolution and Dynamic Kinetic Resolution 1150
32.3.8 Enantioselective Activation and Deactivation 1154
Abbreviations 1156
References 1156
33 Rhodium-Catalyzed Enantioselective Hydrogenation of Functionalized Ketones
André Mortreux and Abdallah Karim 		1165
33.1 Introduction 1165
33.2 Basic Principles of Ketone Hydrogenation on Rhodium Catalysts 1166
33.3 Enantioselective Hydrogenation of Ketoesters 1166
33.3.1 Enantioselective Hydrogenation of Ketopantoyllactone (KPL) 1166
33.3.2 Hydrogenation of Ketoesters and Ketoamides 1172
33.3.2.1 -Ketoesters and Ketoamides 1172
33.3.2.2 , -Diketoesters 1176
33.3.3 Hydrogenation of Amino Ketones 1177
33.3.3.1 -Amino Ketones 1177
33.3.3.2 - and -Amino Ketones 1184
33.4 Enantioselective Hydrogenation of Fluoroketones 1186
33.5 Conclusions 1188
Abbreviations and Acronyms 1189
References 1189
34 Enantioselective Hydrogenation of C=N Functions and Enamines
Felix Spindler and Hans-Ulrich Blaser 		1193
34.1 Introduction 1193
34.2 Chiral Ligands 1195
34.3 N-Aryl Imines 1197
34.4 N-Alkyl Imines 1200
34.5 Cyclic Imines and Heteraromatic Substrates 1202
34.6 Miscellaneous C=N--X Systems 1204
34.7 Enamines 1206
34.8 Mechanistic Aspects 1207
34.9 Alternative Reduction Systems 1209
34.10 Assessment of Catalysts and Conclusions 1210
34.10.1 Iridium Complexes 1210
34.10.2 Rhodium Complexes 1211
34.10.3 Ruthenium Complexes 1211
34.10.4 Titanium Complexes 1211
Abbreviations 1212
References 1212
35 Enantioselective Transfer Hydrogenation
A. John Blacker 		1215
35.1 Introduction 1215
35.2 Homogenous Metal Catalysts 1216
35.2.1 Early studies 1216
35.2.2 Group VIII Metal Catalysts 1217
35.2.3 Chiral Ligands 1218
35.2.4 Immobilized Ligands 1220
35.2.5 Water-Soluble Ligands 1221
35.2.6 Catalyst Selection 1221
35.2.7 Catalyst Preparation 1222
35.2.8 The Reaction Mechanism 1223
35.3 Hydrogen Donors 1224
35.3.1 The IPA System 1224
35.3.2 The TEAF System 1225
35.3.3 Other Hydrogen Donors 1229
35.4 Substrates and Products 1229
35.4.1 Aldehydes 1229
35.4.2 Ketones 1229
35.4.3 Aldimines 1231
35.4.4 Ketimines 1232
35.4.5 Alkenes 1235
35.5 Solvents 1235
35.6 Reaction Conditions, Optimization, and Scale-Up 1236
35.6.1 Temperature 1236
35.6.2 Productivity 1237
35.6.3 Reaction Control 1238
35.6.4 Large-Scale Processes 1239
35.7 Discussion 1239
Abbreviations 1240
References 1241
36 High-Throughput Experimentation and Ligand Libraries
Johannes G. de Vries and Laurent Lefort 		1245
36.1 Introduction 1245
36.2 High-Throughput Experimentation 1248
36.2.1 Serial Mode 1248
36.2.2 Parallel Experimentation 1249
36.2.3 Combinatorial Protocols 1249
36.3 Generating and Testing Libraries of Catalysts and Ligands 1250
36.3.1 Libraries of Individually Synthesized Ligands 1250
36.3.2 Automated Synthesis of Ligand Libraries 1258
36.3.3 Mixtures of Chiral Monodentate Ligands 1263
36.3.4 Mixtures of Chiral Monodentate Ligands and Nonchiral Ligands 1267
36.3.5 Supramolecular Approaches to Ligand Libraries 1270
36.4 Methodology for Testing Catalysts 1272
36.5 High-Throughput Analysis 1273
36.6 Conclusions 1274
Abbreviations 1275
References 1275
37 Industrial Applications
Hans-Ulrich Blaser, Felix Spindler, and Marc Thommen 		1279
37.1 Introduction and Scope of the Chapter 1279
37.2 Requirements for Technical-Scale Applications 1280
37.2.1 Catalyst Performance 1281
37.2.2 Availability and Cost of the Catalyst 1281
37.2.3 Development Time 1282
37.3 Process Development and Equipment 1283
37.4 Industrial Processes: General Comments 1284
37.5 Chemo- and Diastereoselective Hydrogenations 1286
37.6 Enantioselective Hydrogenation of C=C Bonds 1287
37.6.1 Dehydro a-Amino Acid Derivatives 1287
37.6.1.1 L-Dopa (Monsanto, VEB Isis-Chemie) 1288
37.6.1.2 Aspartame (Enichem/Anic, Degussa) 1289
37.6.1.3 Various Pilot- and Bench-Scale Processes for a-Amino Acid Derivatives 1289
37.6.2 Dehydro -Amino Acid Derivatives 1292
37.6.3 Simple Enamides and Enol Acetates 1293
37.6.4 Itaconic Acid Derivatives 1293
37.6.5 Allylic Alcohols and a,b-Unsaturated Acids 1294
37.6.5.1 Allylic Alcohols 1295
37.6.5.2 , -Unsaturated Acids 1296
37.6.6 Miscellaneous C=C Systems 1298
37.6.6.1 Hydrogenation of a Biotin Intermediate (Lonza) 1299
37.6.6.2 Synthesis of (+)-Methyl cis-Dihydrojasmonate (Firmenich) 1300
37.6.6.3 Intermediate for Tipranavir (Chirotech) 1300
37.6.6.4 Various C=C Substrates 1302
37.7 Enantioselective Hydrogenation of C=O Bonds 1302
37.7.1 -Functionalized Ketones 1302
37.7.2 -Functionalized Ketones 1305
37.7.3 Aromatic Ketones 1307
37.8 Enantioselective Hydrogenation of C=N Bonds 1308
37.9 Ligands and Metal Complexes for Large-Scale Applications 1311
37.9.1 Companies Offering Services, Technology, Ligands and Catalysts 1312
37.9.2 Chiral Ligands with Established Industrial Performance 1313
37.9.3 Metal Complexes and Anions 1313
37.9.4 Intellectual Property Aspects 1317
37.10 Conclusions and Future Developments 1317
Acknowledgments 1319
Abbreviations 1319
References 1319
Part V Phase Separation in Homogeneous Hydrogenation  
38 Two-Phase Aqueous Hydrogenations
Ferenc Joó and Ágnes Kathó 		1327
38.1 Introduction 1327
38.2 Two-Phase Hydrogenation of Alkenes, Alkynes, and Arenes 1334
38.3 Enantioselective Hydrogenation of Alkenes in Two-Phase Aqueous Systems 1338
38.4 Aqueous Two-Phase Hydrogenation of Aldehydes and Ketones 1344
38.5 Aqueous Two-Phase Hydrogenations of Nitro-Compounds, Imines, Nitriles, Oximes, and Heteroaromatics 1352
38.6 Conclusions 1354
Abbreviations 1355
References 1355
39 Supercritical and Compressed Carbon Dioxide as Reaction Medium and Mass Separating Agent for Hydrogenation Reactions using Organometallic Catalysts
Walter Leitner 		1361
39.1 Introduction 1361
39.2 The Molecular and Reaction Engineering Basis of Organometallic-Catalyzed Hydrogenations using Compressed and scCO2 1362
39.2.1 Control of Hydrogen Availability 1362
39.2.2 Catalyst Recycling and Immobilization 1363
39.2.2.1 Solubility Control for Separation 1364
39.2.2.2 Membrane Separation 1364
39.2.2.3 Biphasic Liquid/Supercritical Systems 1364
39.2.2.4 Inverted Biphasic Systems 1364
39.2.2.5 Solid-Supported Catalysts 1365
39.2.3 Catalytic Systems for Hydrogenation using SCFs, and their Synthetic Applications 1365
39.2.4 Mechanistic Aspects 1371
39.3 Conclusions and Outlook 1373
Abbreviations 1374
References 1374
40 Fluorous Catalysts and Fluorous Phase Catalyst Separation for Hydrogenation Catalysis
Elwin de Wolf and Berth-Jan Deelman 		1377
40.1 Introduction 1377
40.2 Catalysts Based on Fluorous Alkylphosphines, -Phosphinites, -Phosphonites, and -Phosphites 1378
40.3 Catalysts Based on Perfluoroalkyl-Substituted Arylphosphines 1380
40.4 Fluorous Anions for the Separation of Cationic Hydrogenation Catalysts 1384
40.5 Catalysts Based on Nonphosphorus Ligands 1386
40.6 Enantioselective Hydrogenation Catalysts 1386
40.7 Conclusions 1386
Abbreviations 1387
References and Notes 1387
41 Catalytic Hydrogenation using Ionic Liquids as Catalyst Phase
Peter Wasserscheid and Peter Schulz 		1389
41.1 Introduction to Ionic Liquids 1389
41.2 Homogeneous Catalyzed Hydrogenation in Biphasic LiquidLiquid Systems 1394
41.2.1 Hydrogenation of Olefins 1394
41.2.2 Hydrogenation of Arenes 1397
41.2.3 Hydrogenation of Polymers 1400
41.2.4 Stereoselective Hydrogenation 1401
41.2.5 Ketone and Imine Hydrogenation in Ionic Liquids 1407
41.2.6 Imine Hydrogenation 1411
41.3 Homogeneous Catalyzed Hydrogenation in Biphasic Ionic Liquid/Supercritical (sc)CO2 System 1412
41.4 Supported Ionic Liquid Phase Catalysis 1413
41.5 Conclusion 1416
Abbreviations 1417
References 1417
42 Immobilization Techniques
Imre Tóth and Paul C. van Geem 		1421
42.1 Introduction 1421
42.2 Engineering and Experimental Aspects 1422
42.3 Immobilization Methods 1424
42.3.1 Physical Methods of Immobilization 1426
42.3.1.1 Physisorption of Metal Complexes 1427
42.3.1.2 Weak Chemisorption: Supported Hydrogen-Bonded (SHB) Catalysts 1427
42.3.2 Encapsulated Homogeneous Catalysts 1430
42.3.2.1 Synthesis of SIB Catalysts 1431
42.3.2.2 Application of SIB Catalysts 1433
42.3.3 Catalysts Entangled in a Polymer 1434
42.3.4 Catalyst Dissolved in a Supported Liquid-Phase 1435
42.3.4.1 Supported Aqueous-Phase Catalysis 1436
42.3.4.2 Hybrid SLP Systems 1437
42.3.5 Covalently Bound Metal Centers 1438
42.3.6 Covalent Attachment of Ligands 1439
42.3.6.1 Grafting to Oxide Supports 1440
42.3.6.2 SolGel Method 1441
42.3.6.3 Anchoring with Organic Phosphonates 1442
42.3.6.4 Attachment to Polymer Supports 1444
42.3.6.4.1 Functionalized Polymers as Supports 1444
42.3.6.4.2 Enzymes as Support 1448
42.3.6.4.3 Functionalized Monomers 1448
42.3.6.4.4 Dendrimers as Supports: Membrane Filtration 1453
42.3.6.4.5 Grafting to Polymers 1454
42.3.7 Ionic Bonding of Metals to Supports 1455
42.3.7.1 Ionically Bound Metal Centers on Inorganic Supports 1455
42.3.7.2 Ionically Bound Metal Centers on Polymer Supports 1456
42.3.8 Attachment of Ligands via Ion Exchange 1457
42.4 Catalyst Deactivation 1461
42.5 Conclusions 1462
42.6 Outlook 1462
Abbreviations 1463
References 1463
Part VI Miscellaneous Topics in Homogeneous Hydrogenation  
43 Transition Metal-Catalyzed Regeneration of Nicotinamide Cofactors
Stephan Lütz 		1471
43.1 Introduction 1471
43.2 Enzymatic Cofactor Regeneration 1474
43.3 Electrochemical Cofactor Regeneration 1475
43.4 Chemical Cofactor Regeneration 1477
43.5 Other Chemical Cofactor Regeneration Procedures 1479
43.6 Conclusions and Outlook 1479
Acknowledgments 1480
Abbreviations 1480
References 1480
44 Catalyst Inhibition and Deactivation in Homogeneous Hydrogenation
Detlef Heller, André H.M. deVries, and Johannes G. deVries 		1483
44.1 Introduction 1483
44.2 Mechanisms of Catalyst Inhibition 1484
44.3 Induction Periods 1485
44.3.1 Introduction 1485
44.3.2 Induction Period Caused by Slow Hydrogenation of COD or NBD 1486
44.4 Substrate and Product Inhibition 1494
44.5 Reversible Inhibition Caused by Materials that can Function as Ligand 1499
44.5.1 Catalyst Deactivation Caused by Solvents 1500
44.5.2 Catalyst Inhibition Caused by Compounds Containing Heteroatoms 1503
44.5.3 Inhibition by CO and sources of CO 1504
44.5.4 Inhibition by Acids and Bases 1505
44.6 Irreversible Deactivation 1507
44.6.1 Inhibition by Anions 1507
44.6.2 Inhibition by Oxidation and by Ligand Modification 1507
44.6.3 Formation of Dimers, Trimers, Clusters, Colloids, and Solids 1509
44.7 Conclusions 1512
Abbreviations 1513
References 1513
45 Chemical Reaction Engineering Aspects of Homogeneous Hydrogenations
Claude de Bellefon and Nathalie Pestre 		1517
45.1 Introduction 1517
45.2 Fundamentals 1518
45.2.1 Basics of Mass Transfer in GasLiquid Systems 1518
45.2.2 Physical and Chemical Data for Hydrogenations 1521
45.2.2.1 Heat of Reaction 1522
45.2.2.2 Solubility 1522
45.2.2.3 Diffusivity 1525
45.2.3 Coupling Between Mass Transfer and a Single Homogeneous Irreversible Reaction 1526
45.2.4 Coupling of Reaction and Mass Transfer in Ideal Reactors 1533
45.2.4.1 Mass Balance for a Batch Reactor 1534
45.2.4.2 Mass Balance for a CSTR Reactor 1535
45.2.4.2.1 Simplified Mass Balances 1535
45.2.4.3 Mass Balance for a Plug Flow Reactor 1536
45.3 Industrial Reactor and Scale-Up Issues 1536
45.4 Future Developments 1541
Nomenclature 1542
Abbreviations 1544
References 1544
  Subject Index 1547

 
Order
Online book
Table of contents
Short description
Detailed description
Reviews
Author information
Author affiliation

Related Books

Aromaticity and Other Conjugation Effects

Aromaticity and Other Conjugation Effects

Handbook of Green Chemistry - Green Processes


[more >>]

Related Journals

Angewandte Chemie

Angewandte Chemie International Edition

Chemie Ingenieur Technik


[more>>]

Special Offers

Christie, Daniel J. (ed.)

The Encyclopedia of Peace Psychology
385.- Euro
valid until
31 March 2012

[more offers >>]


 

        

Tell a friend          RSS Feeds             Print-Version

©2012 Wiley-VCH Verlag GmbH & Co. KGaA - Provider
http://www.wiley-vch.de - mailto: info@wiley-vch.de
Data Protection