均相催化PDF电子书下载

1．INTRODUCTION 1

1.1 CATALYSIS 1

1.2 HOMOGENEOUS CATALYSIS 6

1.3 HISTORICAL NOTES ON HOMOGENEOUS CATALYSIS 7

1.4 CHARACTERISATION OF THE CATALYST 8

1.5 LIGAND EFFECTS 10

1.5.1 Phosphines and phosphites:electronic effects 10

1.5.2 Phosphines and phosphites:steric effects 12

1.5.3 Linear Free Energy Relationships 14

1.5.4 Phosphines and phosphites:bite angle effects 16

1.6 LIGANDS ACCORDING TO DONOR ATOMS 20

1.6.1 Anionic and neutral hydrocarbyl groups 20

1.6.2 Alkoxy and imido groups as anionic ligands 21

1.6.3 Amines,imines,oxazolines and related ligands 21

1.6.4 Phosphines,phosphites,phosphorus amides,phospholes and related ligands 23

1.6.5 Carbenes,carbon monoxide 24

1.6.6 Common anions 25

2．ELEMENTARY STEPS 29

2.1 CREATION OF A"VACANT"SITE AND CO-ORDINATION OF THE SUBSTRATE 29

2.2 INSERTION VERSUS MIGRATION 30

2.3 β-ELIMINATION AND DE-INSERTION 35

2.4 OXIDATIVE ADDITION 36

2.5 REDUCTIVE ELIMINATION 39

2.6 α-ELIMINATION REACTIONS 41

2.7 CYCLOADDITION REACTIONS INVOLVING A METAL 42

2.8 ACTIVATION OF A SUBSTRATE TOWARD NUCLEOPHILIC ATTACK 44

2.8.1 Alkenes 44

2.8.2 Alkynes 45

2.8.3 Carbon monoxide 45

2.8.4 Other substrates 46

2.9 σ-BOND METATHESIS 48

2.10 DIHYDROGEN ACTIVATION 48

2.11 ACTIVATION BY LEWIS ACIDS 50

2.11.1 Diels-Alder additions 51

2.11.2 Epoxidation 51

2.11.3 Ester condensation 52

2.12 CARBON-TO-PHOSPHORUS BOND BREAKING 52

2.13 CARBON-TO-SULFUR BOND BREAKING 55

2.14 RADICAL REACTIONS 57

3．KINETICS 63

3.1 INTRODUCTION 63

3.2 TWO-STEP REACTION SCHEME 63

3.3 SIMPLIFICATIONS OF THE RATE EQUATION AND THE RATE-DETERMINING STEP 64

3.4 DETERMINING THE SELECTIVITY 68

3.5 COLLECTION OF RATE DATA 71

3.6 IRREGULARITIES IN CATALYSIS 72

4．HYDROGENATION 75

4.1 WILKINSON'S CATALYST 75

4.2 ASYMMETRIC HYDROGENATION 77

4.2.1 Introduction 77

4.2.2 Cinnamic acid derivatives 79

4.2.3 Chloride versus weakly coordinating anions;alkylphosphines versus arylphosphines 86

4.2.4 Incubation times 86

4.3 OVERVIEW OF CHIRAL BIDENTATE LIGANDS 86

4.3.1 DuPHOS 86

4.3.2 BINAP catalysis 87

4.3.3 Chiral ferrocene based ligands 89

4.4 MONODENTATE LIGANDS 90

4.5 NON-LINEAR EFFECTS 93

4.6 HYDROGEN TRANSFER 94

5．ISOMERISATION 101

5.1 HYDROGEN SHIFTS 101

5.2 ASYMMETRIC ISOMERISATION 103

5.3 OXYGEN SHIFTS 105

6．CARBONYLATION OF METHANOL AND METHYL ACETATE 109

6.1 ACETIC ACID 109

6.2 PROCESS SCHEME MONSANTO PROCESS 114

6.3 ACETIC ANHYDRIDE 116

6.4 OTHER SYSTEMS 118

6.4.1 Higher alcohols 118

6.4.2 Phosphine-modified rhodium catalysts 119

6.4.3 Other metals 122

7．COBALT CATALYSED HYDROFORMYLATION 125

7.1 INTRODUCTION 125

7.2 THERMODYNAMICS 126

7.3 COBALT CATALYSED PROCESSES 126

7.4 COBALT CATALYSED PROCESSES FOR HIGHER ALKENES 128

7.5 KUHLMANN COBALT HYDROFORMYLATION PROCESS 130

7.6 PHOSPHINE MODIFIED COBALT CATALYSTS:THE SHELL PROCESS 131

7.7 COBALT CARBONYL PHOSPHINE COMPLEXES 132

7.7.1 Carbonyl species 132

7.7.2 Phosphine derivatives 135

8．RHODIUM CATALYSED HYDROFORMYLATION 139

8.1 INTRODUCTION 139

8.2 TRIPHENYLPHOSPHINE AS THE LIGAND 141

8.2.1 The mechanism 141

8.2.2 Ligand effects and kinetics 144

8.2.3 Regioselectivity 147

8.2.4 Process description,rhodium-tpp 149

8.2.5 Two-phase process,tppts:Ruhrchemie/Rh？ne-Poulenc 150

8.2.6 One-phase catalysis,two-phase separation 152

8.3 DIPHOSPHINES AS LIGANDS 153

8.3.1 Xantphos ligands:tuneable bite angles 155

8.4 PHOSPHITES AS LIGANDS 161

8.4.1 Electronic effects 161

8.4.2 Phosphites:steric effects 162

8.5 DIPHOSPHITES 163

8.6 ASYMMETRIC HYDROFORMYLATION 166

8.6.1 Rhodium catalysts:diphosphites 166

8.6.2 Rhodium catalysts:phosphine-phosphite ligands 168

9．ALKENE OLIGOMERISATION 175

9.1 INTRODUCTION 175

9.2 SHELL-HIGHER-OLEFINS-PROCESS 176

9.2.1 Oligomerisation 176

9.2.2 Separation 180

9.2.3 Purification,isomerisation,and metathesis 180

9.2.4 New catalysts 181

9.3 ETHENE TRIMERISATION 184

9.4 OTHER ALKENE OLIGOMERISATION REACTIONS 187

10．PROPENE POLYMERISATION 191

10.1 INTRODUCTION TO POLYMER CHEMISTRY 191

10.1.1 Introduction to Ziegler Natta polymerisation 193

10.1.2 History of homogeneous catalysts 196

10.2 MECHANISTIC INVESTIGATIONS 199

10.2.1 Chain-end control:syndiotactic polymers 199

10.2.2 Chain-end control:isotactic polymers 201

10.3 ANALYSIS BY 13 C NMR SPECTROSCOPY 202

10.3.1 Introduction 202

10.3.2 Chain-end control 204

10.3.3 Site control mechanism 204

10.4 THE DEVELOPMENT OF METALLOCENE CATALYSTS 206

10.4.1 Site control:isotactic polymers 206

10.4.2 Site control:syndiotactic polymers 209

10.4.3 Double stereoselection:chain-end and site control 211

10.5 AGOSTIC INTERACTIONS 212

10.6 THE EFFECT OF DIHYDROGEN 214

10.7 FURTHER WORK USING PROPENE AND OTHER ALKENES 215

10.8 NON-METALLOCENE ETM CATALYSTS 220

10.9 LATE TRANSITION METAL CATALYSTS 222

11．HYDROCYANATION OF ALKENES 229

11.1 THE ADIPONITRILE PROCESS 229

11.2 LIGAND EFFECTS 233

12．PALLADIUM CATALYSED CARBONYLATIONS OF ALKENES 239

12.1 INTRODUCTION 239

12.2 POLYKETONE 239

12.2.1 Background and history 239

12.2.2 Elementary steps:initiation 241

12.2.3 Elementary steps:migration reactions 244

12.2.4 Elementary steps:chain termination,chain transfer 250

12.2.5 Elementary steps:ester formation as chain termination 252

12.3 LIGAND EFFECTS ON CHAIN LENGTH 256

12.3.1 Polymers 256

12.3.2 Ligand effects on chain length:Propanoate 258

12.3.3 Ligand effects on chain length:Oligomers 261

12.4 ETHENE/PROPENE/CO TERPOLYMERS 262

12.5 STEREOSELECTIVE STYRENE/CO COPOLYMERS 263

13．PALLADIUM CATALYSED CROSS-COUPLING REACTIONS 271

13.1 INTRODUCTION 271

13.2 ALLYLIC ALKYLATION 273

13.3 HECK REACTION 281

13.4 CROSS-COUPLING REACTION 286

13.5 HETEROATOM-CARBON BOND FORMATION 290

13.6 SUZUKI REACTION 294

14．EPOXIDATION 299

14.1 ETHENE AND PROPENE OXIDE 299

14.2 ASYMMETRIC EPOXIDATION 301

14.2.1 Introduction 301

14.2.2 Katsuki-Sharpless asymmetric epoxidation 301

14.2.3 The Jacobsen asymmetric epoxidation 305

14.3 ASYMMETRIC HYDROXYLATION OF ALKENES WITH OSMIUM TETROXIDE 308

14.3.1 Stoichiometric reactions 308

14.3.2 Catalytic reactions 312

14.4 JACOBSEN ASYMMETRIC RING-OPENING OF EPOXIDES 314

14.5 EPOXIDATIONS WITH DIOXYGEN 316

15．OXIDATION WITH DIOXYGEN 319

15.1 INTRODUCTION 319

15.2 THE WACKER REACTION 320

15.3 WACKER TYPE REACTIONS 324

15.4 TEREPHTHALIC ACID 327

15.5 PPO 332

16．ALKENE METATHESIS 337

16.1 INTRODUCTION 337

16.2 THE MECHANISM 339

16.3 REACTION OVERVIEW 343

16.4 WELL-CHARACTERISED TUNGSTEN AND MOLYBDENUM CATALYSTS 344

16.5 RUTHENIUM CATALYSTS 346

16.6 STEREOCHEMISTRY 349

16.7 CATALYST DECOMPOSITION 350

16.8 ALKYNES 352

16.9 INDUSTRIAL APPLICATIONS 354

17．ENANTIOSELECTIVE CYCLOPROPANATION 359

17.1 INTRODUCTION 359

17.2 COPPER CATALYSTS 360

17.3 RHODIUM CATALYSTS 364

17.3.1 Introduction 364

17.3.2 Examples of rhodium catalysts 367

18．HYDROSILYLATION 371

18.1 INTRODUCTION 371

18.2 PLATINUM CATALYSTS 373

18.3 ASYMMETRIC PALLADIUM CATALYSTS 378

18.4 RHODIUM CATALYSTS FOR ASYMMETRIC KETONE REDUCTION 380

19．C-H FUNCTIONALISATION 387

19.1 INTRODUCTION 387

19.2 ELECTRON-RICH METALS 389

19.3 HYDROGEN TRANSFER REACTIONS OF ALKANES 394

19.4 BORYLATION OF ALKANES 395

19.5 THE MURAI REACTION 396

19.6 CATALYTIC σ-BOND METATHESIS 397

19.7 ELECTROPHILIC CATALYSTS 397

SUBJECT INDEX 403