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More About This Title Green Biocatalysis
English
English
English
About the Editor xxiii
Contributors xxv
Chapter 1 Biocatalysis and Green Chemistry 1
Roger A. Sheldon
1.1 Introduction to Sustainable Development and Green Chemistry 1
1.2 Green Chemistry Metrics 2
1.3 Environmental Impact and Sustainability Metrics 4
1.4 Solvents 5
1.5 The Role of Catalysis 6
1.6 Biocatalysis and Green Chemistry 6
1.7 Examples of Green Biocatalytic Processes 8
1.8 Conclusions and Future Prospects 13
Chapter 2 Enzymatic Synthesis of Chiral Amines using ω-Transaminases, Amine Oxidases, and the Berberine Bridge Enzyme 17
Eduardo Busto, Robert C. Simon, Nina Richter, and Wolfgang Kroutil
2.1 Introduction 17
2.2 Synthesis of Chiral Amines using ω]Transaminases 18
2.3 Amine Oxidases 34
2.4 Berberine Bridge Enzymes 50
2.5 Conclusions 52
Chapter 3 Decarboxylation and Racemization of Unnatural Compounds using Artificial Enzymes Derived from Arylmalonate Decarboxylase 59
Kenji Miyamoto
3.1 Introduction 59
3.2 Discovery of a Bacterial α]Aryl]α]Methylmalonate Decarboxylase 61
3.3 Purification and Characterization of the Decarboxylase (Amdase) 61
3.4 Cloning of the Amdase Gene 62
3.5 Stereochemical Course of Amdase]Catalyzed Decarboxylation 62
3.6 Directed Evolution of Amdase to an Artificial Profen Racemase 63
3.7 Inversion of Enantioselectivity Dramatically Improves Catalytic Activity 65
3.8 Future Prospects 68
Chapter 4 Green Processes for the Synthesis of Chiral Intermediates for the Development of Drugs 71
Ramesh N. Patel
4.1 Introduction 71
4.2 Saxagliptin: Enzymatic Synthesis of (S)]N]Boc]3]Hydroxyadamantylglycine 71
4.3 Sitagliptin: Enzymatic Synthesis of Chiral Amine 72
4.4 Vanlev: Enzymatic Synthesis of (S)]6]Hydroxynorleucine 73
4.5 Vanlev: Enzymatic Synthesis of Allysine Ethylene Acetal 74
4.6 Vanlev: Enzymatic Synthesis of Thiazepine 74
4.7 Tigemonam: Enzymatic Synthesis of (S)]β]Hydroxyvaline 76
4.8 Autoimmune Diseases: Enzymatic Synthesis of (S)]Neopentylglycine 76
4.9 Atazanavir: Enzymatic Synthesis of (S)]Tertiary Leucine 77
4.10 Thrombin Inhibitor (Inogatran): Synthesis of (R)]Cyclohexylalanine 78
4.11 Gamma Secretase Inhibitor: Enzymatic Synthesis of (R)]5,5,5]Trifluoronorvaline 79
4.12 NK1/NK2 Dual Antagonists: Enzymatic Desymmetrization of Diethyl 3][3′,4′]Dichlorophenyl] Glutarate 80
4.13 Pregabalin: Enzymatic Synthesis of Ethyl (S)]3]Cyano]5]Methylhexanoate 81
4.14 Chemokine Receptor Modulator: Enzymatic Synthesis of (1S,2R)]2](Methoxycarbonyl)-Cyclohex]4]ene]1]Carboxylic Acid 82
4.15 Enzymatic Synthesis of (3S,5R)]3](Aminomethyl)]5]Methyloctanoic Acid 82
4.16 Atorvastatin (Lipitor): Enzymatic Desymmetrization of 3]Hydroxyglutaronitrile 83
4.17 Anticancer Drugs: Enzymatic Synthesis of Taxane Side Chain 84
4.18 Antidiabetic and CNS Drugs: Enzymatic Hydrolysis of Dimethyl Bicyclo[2.2.1] Heptane]1,4]Dicarboxylate 85
4.19 Clopidogrel (Plavix): Enzymatic Preparation of 2]Chloromandelic Acid Esters 85
4.20 Antiviral Drug: Regioselective Enzymatic Acylation of Ribavirin 86
4.21 Anticholesterol Drug: Enzymatic Acylation of Alcohol 87
4.22 Saxagliptin: Enzymatic Synthesis of (5S)]4,5]Dihydro]1H]Pyrrole]1,5 Dicarboxylic Acid, 1](1,1]Dimethylethyl)]5]Ethyl Ester 88
4.23 Montelukast: Synthesis of Intermediate for LTD4 Antagonists 89
4.24 Atazanavir: Enzymatic Synthesis of (1S,2R)][3]Chloro]2]Hydroxy]1 (Phenylmethyl) Propyl]]Carbamic Acid,1,1]Dimethyl]Ethyl Ester 90
4.25 Atorvastatin: Enzymatic Synthesis of (R)]4]Cyano]3]Hydroxybutyrate 91
4.26 Antianxiety Drug: Enzymatic Synthesis of 6]Hydroxybuspirone 92
4.27 Protease Inhibitor: Enzymatic Synthesis of (R)]3](4]Fluorophenyl)]2]Hydroxy Propionic Acid 93
4.28 Dermatological and Anticancer Drugs: Enzymatic Synthesis of 2](R)]Hydroxy]2](1′,2′,3′, 4′]Tetrahydro]1′,1′,4′,4′]Tetramethyl]6′]Naphthalenyl) Acetate 94
4.29 Antipsychotic Drug: Enzymatic Reduction of 1](4]Fluorophenyl)4][4](5]Fluoro]2]Pyrimidinyl)1]Piperazinyl]]1]Butanone 95
4.30 Cholesterol]Lowering Agents: Enzymatic Synthesis of (3S,5R)]Dihydroxy]6](Benzyloxy) Hexanoic Acid, Ethyl Ester 95
4.31 Antimigraine Drugs: Enzymatic Synthesis of (R)]2]Amino]3](7]Methyl]1H]Indazol]5]yl) Propanoic Acid 96
4.32 Antidiabetic Drug (GLP]1 Mimics): Enzymatic Synthesis of (S)]Amino]3][3]{6](2]Methylphenyl)} Pyridyl]]Propionic Acid 97
4.33 Ephedrine: Synthesis of (R)]Phenylacetylcarbinol 98
4.34 Zanamivir: Enzymatic Synthesis of N]Acetylneuraminic Acid 99
4.35 Epivir: Enzymatic Deamination Process for the Synthesis of (2′R]cis)]2′]Deoxy]3]Thiacytidine 100
4.36 HMG]CoA Reductase Inhibitors: Aldolase]Catalyzed Synthesis of Chiral Lactol 101
4.37 Boceprevir: Oxidation of 6,6]Dimethyl]3]Azabicyclo[3.1.0]Hexane by Monoamine Oxidase 102
4.38 Crixivan: Enzymatic Synthesis of Indandiols 103
4.39 Potassium Channel Opener: Preparation of Chiral Epoxide and trans]Diol 104
4.40 Epothilones (Anticancer Drugs): Epothilone B and Epothilone F 105
4.41 β]Adrenergic Blocking Agents: Synthesis of Intermediates for Propranolol and Denopamine 106
4.42 Conclusion 106
Chapter 5 Dynamic Kinetic Resolution of Alcohols, Amines, and Amino Acids 115
Jusuk Lee, Yoon Kyung Choi, Jaiwook Park, and Mahn]Joo Kim
5.1 Introduction 115
5.2 Dynamic Kinetic Resolution of Secondary Alcohols 119
5.3 Dynamic Kinetic Resolution of Amines and Amino Acids 133
5.4 Applications of Dynamic Kinetic Resolution 139
5.5 Summary 145
Appendix: List of Abbreviations 145
Chapter 6 Recent Developments in Flavin-Based Catalysis: Enzymatic Sulfoxidation 149
Patricia B. Brondani, Marco W. Fraaije, and Gonzalo de Gonzalo
6.1 Introduction 149
6.2 Enzymatic Sulfoxidation Catalyzed by Flavoprotein Oxidases 150
6.3 Use of Flavoprotein Monooxygenases for the Synthesis of Chiral Sulfoxides 151
6.4 Asymmetric Sulfoxidation using Flavins as Catalysts 160
6.5 Summary and Outlook 162
Chapter 7 Development of Chemoenzymatic Processes: An Industrial Perspective 165
Rajesh Kumar, Carlos Martinez, Van Martin, and John Wong
7.1 Introduction 165
7.2 Synthetic Route Design and Integration of Biocatalysis 166
7.3 Screening and Biocatalyst Selection 169
7.4 Chemoenzymatic Process Development 169
7.5 Conclusions 176
Chapter 8 Epoxide Hydrolases and their Application in Organic Synthesis 179
Alain Archelas, Gilles Iacazio, and Michael Kotik
8.1 Introduction 179
8.2 Sources and Reaction Mechanism of EHs 181
8.3 Directed Evolution and Genetic Engineering of EHs 183
8.4 Immobilized EHs and Reactions in Nonaqueous Media 186
8.5 Monofunctional Epoxides as Chiral Building Blocks for the Synthesis of Biologically Active Compounds 188
8.6 Preparation of Valuable Chiral Building Blocks for the Synthesis of Biologically Active Compounds Starting from Bifunctional Epoxides 204
8.7 Application to Natural Product Synthesis 210
8.8 Bienzymatic Process Implying One Epoxide Hydrolase 216
8.9 Conclusions 219
Chapter 9 Enantioselective Acylation of Alcohol and Amine Reactions in Organic Synthesis 231
Vicente Gotor]Fernández and Vicente Gotor
9.1 Introduction 231
9.2 Enantioselective Acylation of Alcohols 234
9.3 Acylation of Amines 248
9.4 Conclusions 260
Chapter 10 Recent Advances in Enzyme-Catalyzed Aldol Addition Reactions 267
Pere Clapés
10.1 Introduction 267
10.2 Pyruvate-Dependent Aldolases 269
10.3 Dihydroxyacetone Phosphate (DHAP)-Dependent Aldolases, d-Fructose-6-Phosphate Aldolase (FSA) and Transaldolases 276
10.4 Threonine Aldolases 287
10.5 Aldol Type Reactions Catalyzed by Non]Aldolases 293
10.6 Computational De Novo Enzyme Design 294
10.7 Conclusions and Perspectives 295
Chapter 11 Enzymatic Asymmetric Reduction of Carbonyl Compounds 307
Tomoko Matsuda, Rio Yamanaka, and Kaoru Nakamura
11.1 Introduction 307
11.2 Mechanisms 307
11.3 Preparation of Biocatalysts 309
11.4 Solvent Engineering 316
11.5 Examples for Biocatalytic Asymmetric Reductions 317
11.6 Conclusions 325
Chapter 12 Nitrile]Converting Enzymes and their Synthetic Applications 331
Ludmila Martínková
12.1 Introduction 331
12.2 Screening Methodology 332
12.3 Nitrilases 333
12.4 Nitrile Hydratases 340
12.5 Conclusions 343
Acknowledgements 343
Chapter 13 Biocatalytic Epoxidation for Green Synthesis 351
Hui Lin, Meng]Yu Xu, Yan Liu, and Zhong]Liu Wu
13.1 Introduction 351
13.2 Enzymes for Asymmetric Epoxidation 352
13.3 Application of Bioepoxidation in Organic Synthesis 354
13.4 Protein Engineering for Biocatalytic Epoxidation Reaction 362
13.5 Conclusions and Outlook 367
Acknowledgments 368
Chapter 14 Dynamic Kinetic Resolution via Hydrolase–Metal Combo Catalysis 373
Pilar Hoyos, Vittorio Pace, María J. Hernáiz, and Andrés R. Alcántara
14.1 Introduction 373
14.2 DKR of Secondary Alcohols 374
14.3 DKR of Amines 386
14.4 Conclusion 391
Chapter 15 Discovery and Engineering of Enzymes for Peptide Synthesis and Activation 397
Ana Toplak, Muhammad I. Arif, Bian Wu, and Dick B. Janssen
15.1 Introduction 397
15.2 Classification of Enzymes for Peptide Coupling 399
15.3 Serine and Cysteine Proteases for Peptide Synthesis 402
15.4 Protease Discovery 409
15.5 Proteases Engineered for Improved Synthesis 410
15.6 Enzymes for Peptide Terminal Modification 412
15.7 Conclusions 415
Chapter 16 Biocatalysis for Drug Discovery and Development 421
Youyun Liang, Mingzi M. Zhang, Ee Lui Ang, and Huimin Zhao
16.1 Introduction 421
16.2 Single Enzymatic Reactions 423
16.3 Multienzyme Biocatalytic Reactions 437
16.4 Future Perspective: Biocatalysts for the Pharmaceutical Industry 445
16.5 Conclusion 448
Chapter 17 Application of Aromatic Hydrocarbon Dioxygenases 457
Watumesa A. Tan and Rebecca E. Parales
17.1 Introduction 457
17.2 Challenges in Aromatic Hydrocarbon Dioxygenase Applications 457
17.3 Protein Engineering to Improve Enzymatic Activity and Alter Substrate Specificity 459
17.4 Protein Engineering for the Production of Specific Chemicals 464
17.5 Strain Modification for the Development of New Biodegradation Pathways 467
17.6 Phytoremediation: The Expression of Bacterial Dioxygenases in Plant Systems for Bioremediation Purposes 468
17.7 Concluding Remarks 469
Acknowledgments 469
Chapter 18 Ene]reductases and their Applications 473
Tanja Knaus, Helen S. Toogood, and Nigel S. Scrutton
18.1 Introduction 473
18.2 Substrate Classes and Industrial Applications 474
18.3 Multienzyme Reactions 478
18.4 Alternative Hydride Sources 479
18.5 Improvements of Productivity, Stereoselectivity, and/or Conversion 482
Chapter 19 Recent Developments in Aminopeptidases, Racemases, and Oxidases 489
Yasuhisa Asano, Seiji Okazaki, and Kazuyuki Yasukawa
19.1 Aminopeptidase 489
19.2 Racemase 492
19.3 Amino Acid Oxidase 495
Chapter 20 Biocatalytic Cascades for API Synthesis 503
John M. Woodley
20.1 Introduction 503
20.2 Multienzymatic Biocatalysis 504
20.3 Process Aspects for Multistep Biocatalysis 506
20.4 Process Development 511
20.5 Biocatalytic Cascade Examples 512
20.6 Future Outlook 515
Chapter 21 Yeast-Mediated Stereoselective Synthesis 519
René Csuk
21.1 Introduction 519
21.2 Reductions of Aldehydes and Ketones 521
21.3 Reduction of Thiocarbonyls or Sulfur]Containing Compounds 524
21.4 Reduction of Functionalized Carbonyl and Dicarbonyl Compounds 524
21.5 Reduction of Keto Esters 527
21.6 Hydrolysis of Esters 529
21.7 Immobilized Baker’s Yeast 530
21.8 Whole]Cell Biocatalysis in Ionic Liquids and Deep Eutectic Solvents 531
21.9 C„ŸC Bond]Forming and Breaking Reactions 532
21.10 Miscellaneous Reactions 533
21.11 Conclusions 534
Chapter 22 Biocatalytic Introduction of Chiral Hydroxy Groups using Oxygenases and Hydratases 545
Jun Ogawa, Makoto Hibi, and Shigenobu Kishino
22.1 Introduction 545
22.2 Regio] and Stereoselective Hydroxylation of Propylbenzene and 3]Chlorostyrene by Cytochrome P450 BM]3 and its Mutant 546
22.3 Regio] and Stereoselective Hydroxylation of Aliphatic Amino Acids by Fe(Ii)/α]Ketoglutarate]Dependent Dioxygenases 547
22.4 Regio] and Stereoselective Hydration of Unsaturated Fatty Acids by a Novel Fatty Acid Hydratase 551
22.5 Conclusion 553
Acknowledgment 553
Chapter 23 Asymmetric Synthesis with Recombinant Whole]Cell Catalyst 557
Harald Gröger, Werner Hummel, and Severin Wedde
23.1 Introduction 557
23.2 The Design/Construction of Whole]Cell Catalysts 558
23.3 Biotransformations with Whole]Cell Catalysts 561
23.4 Conclusion 581
Chapter 24 Lipases and Esterases as User-Friendly Biocatalysts in Natural Product Synthesis 587
Kenji Mori
24.1 Introduction 587
24.2 Desymmetrization of Prochiral or meso]Diols and Diacetates 587
24.3 Kinetic Resolution of Racemic Alcohols 592
24.4 Preparation of Enantiopure Intermediate(s) from a Mixture of Stereoisomers 599
24.5 Conclusion 601
Acknowledgments 601
Chapter 25 Hydroxynitrile Lyases for Biocatalytic Synthesis of Chiral Cyanohydrins 603
Romana Wiedner, Helmut Schwab, and Kerstin Steiner
25.1 Introduction 603
25.2 Discovery of Hydroxynitrile Lyases: Bioprospecting 604
25.3 Applications of Hydroxynitrile Lyases 609
25.4 Structural and Mechanistic Aspects 611
25.5 Engineering of Hydroxynitrile Lyases 612
25.6 Reaction Engineering and Reaction Systems 620
25.7 Conclusion 623
Acknowledgment 623
Chapter 26 Biocatalysis: Nitrilases in Organic Synthesis 629
Jin]Song Gong, Jin]Song Shi, and Zheng]Hong Xu
26.1 Introduction 629
26.2 Nitrilase Discovery 630
26.3 Nitrilase Improvement 631
26.4 Applications in Organic Synthesis 635
26.5 Conclusions and Future Prospects 638
Acknowledgments 639
Chapter 27 Biotechnology for the Production of Chemicals, Intermediates, and Pharmaceutical Ingredients 643
Hans]Peter Meyer
27.1 Introduction 643
27.2 Value Chains and Markets 645
27.3 The Toolbox 661
27.4 Sustainability, Green Premium Pricing, and Subsidies 665
27.5 Regulatory Aspects and Public Perception 667
27.6 Innovation (Not Only in the Laboratory!) 669
27.7 Conclusions 670
Acknowledgments 671
Chapter 28 Microbial Transformations of Pentacyclic Triterpenes 675
Robert Azerad
28.1 Introduction 675
28.2 Typical Biotransformations in the Lupane Family 677
28.3 Typical Biotransformations in the Oleane Family 680
28.4 Typical Biotransformations in the Ursane Family 692
28.5 Microbial Transformations of Other Pts 704
28.6 Glycosylations and Deglycosylations 704
28.7 Conclusion and Perspectives 710
Chapter 29 Transaminases and their Applications 715
Sarah-Marie Dold, Christoph Syldatk, and Jens Rudat
29.1 Introduction 715
29.2 General Properties of Transaminases 715
29.3 Synthesis Strategies with Transaminases 719
29.4 Approaches to Optimize the Transaminase]Catalyzed Reactions 735
29.5 Conclusion 743
Index 747
