Table of Contents
Preface vii
1 Introduction and fundamental aspects 1
1.1 General concepts of catalysis 3
1.1.1 Basics of thermodynamics and kinetics for chemical reactions 3
1.1.2 General principles of heterogeneous catalysis 9
1.1.3 Mechanisms and kinetics on catalyst surfaces 11
1.1.4 Characterisation of solid catalysts 15
1.1.5 Terms and definitions 19
1.2 Catalyst preparation 28
1.3 Chemical reactors for catalytic processes 30
1.4 Outlook 33
References 34
2 Heterogeneous hydrogenations 37
2.1 Introduction 37
2.2 Nickel catalysts 43
2.2.1 Hydrogenation of nitrites 43
2.2.2 Hydrogenation of carbonyl groups 50
2.2.3 Hydrogenation of other functional groups 51
2.2.4 Reduction of multiple functional groups in the same reaction 54
2.3 Platinum Group Metal (PGM) based catalysts 55
2.3.1 Palladium catalysts 58
2.3.2 Platinum catalysts 78
2.3.3 Other PGM catalysts 83
2.4 Other metal catalysts 85
2.5 Summary 86
References 86
3 Homogeneous hydrogenations 91
3.1 Introduction 91
3.2 Rh-catalysed hydrogenations 92
3.2.1 (S)-3-(3,4-dihydroxyphenyl)alanine, L-DOPA 92
3.2.2 Menthol (BASF Process) 99
3.2.3 Methylene succinamic acid 102
3.2.4 Aliskiren 103
3.2.5 Pregabalin 107
3.2.6 (+)-Biotin 107
3.2.7 Sitagliptin 109
3.2.8 Pantolactone 111
3.3 Ru-catalysed hydrogenations 112
3.3.1 Hydrogenation of allylic alcohols 112
3.3.2 Pivotal glutarate intermediate for candoxatril 114
3.3.3 Artemisinin 115
3.3.4 Ketone reductions 116
3.3.5 Dynamic kinetic resolution via asymmetric hydrogenation 119
3.4 Ir-catalysed hydrogenation 121
3.4.1 Hydrogenation of imines 121
3.4.2 Hydrogenation of ketones with iridium catalysts 124
3.4.3 Hydrogenation of unfunctionalised doubled bonds 125
3.5 Asymmetric transfer hydrogenation of C=O and C=N 128
3.5.1 Dorzolamide 130
3.5.2 Styrene oxide 131
3.5.3 (R,R)-trans-Actinol for zeaxanthin 131
3.5.4 Almorexant 132
References 133
4 Oxidations 142
4.1 Introduction 142
4.2 Oxidation of alcohols 143
4.3 Oxidation of phenols and aromatic compounds 144
4.4 Oxidation of various C-C bonds 150
4.5 Oxidation for silane production 162
References 164
5 Gas-phase reactions 170
References 180
6 C-C-bond and C-N-bond forming reactions (metal-catalysed) 184
6.1 Introduction and Mizoroki-Heck reactions 184
6.2 Other palladium catalysed C-C bond forming reactions 189
6.2.1 Sonogashira-Hagihara reaction 189
6.2.2 Suzuki-Miyaura-coupling 192
6.2.3 Kumada-Corriu coupling 198
6.3 Carbonylation reactions 199
6.4 Hydroformylation reactions 201
6.5 SHOP process 205
6.6 1,3-Diene functionalisation 207
6.7 Telomerisation 208
6.8 Metathesis 217
6.9 Formation of C-N bonds (Buchwald-Hartwig coupling) 222
References 226
7 Rearrangement reactions 235
7.1 Introduction 235
7.2 Wagner-Meerwein rearrangements 235
7.3 Beckmann rearrangement 237
7.4 [3,3]-Sigmatropic-type rearrangements 237
7.5 The Meyer-Schuster, Rupe-Kambli and Pauling rearrangements 246
7.6 Allylic rearrangements 249
References 254
8 Acid-base-catalysed reactions 257
8.1 Replacement of Brønsted acids 257
8.2 Zeolite-based catalysis 263
8.3 Heteropoly acids (HPAs) 267
8.4 Lewis acids 273
8.5 Base catalysis 280
8.6 Ethynylation 286
8.7 Mannich reactions 288
References 289
9 Phase transfer catalysis (PTC) 296
References 308
10 Biocatalysis 311
10.1 Introduction to biocatalysis 311
10.2 Industrial applications 322
10.2.1 Sauerkraut and ethanol: applications with a long history 322
10.2.2 Sugars and oligosaccharides 325
10.2.3 Organic acids 329
10.2.4 Amino acids 335
10.2.5 Vitamins and carotenoids 341
10.2.6 Active pharmaceutical ingredients 353
10.2.7 Flavour compounds 363
10.2.8 Pesticides 365
10.2.9 Platform chemicals 366
References 370
11 New trends 378
References 383
Index 385
