Practical Methods for Biocatalysis and Biotransformations 3

Dr John Whittall, Centre of Excellence for Biocatalysis, Biotransformations and Biocatalytic Manufacture (CoEBio3), Manchester Interdisciplinary Biocentre, University of Manchester, UK. Dr Peter W Sutton, Senior Scientist, GlaxoSmithKline Research and Development Limited, UK. Dr Wolfgang Kroutil, Department of Chemistry, Organic and Bioorganic Chemistry, University of Graz, Austria.

• List of Contributors ixAbbreviations xxi1 Considerations for the Application of Process Technologies in Laboratory- and Pilot-Scale Biocatalysis for Chemical Synthesis 11.1 Introduction 11.2 Process Intensification and Proposed Scale-Up Concept 21.3 Enabling Technologies 51.4 Enhancing Technologies 201.5 Conclusion 28References 282 Cytochrome P450 (CYP) Progress in Biocatalysis for Synthetic Organic Chemistry 312.1 Introduction 312.2 CYP Development 322.3 Recent Developments 342.4 Conclusion 41References 413 Use of Hydrolases and Related Enzymes for Synthesis 433.1 Continuous-Flow Reactor-Based Enzymatic Synthesis of Phosphorylated Compounds on a Large Scale 433.2 Deracemization of sec-Alcohols via Enantio-Convergent Hydrolysis of rac-Sulfate Esters 453.3 Dynamic Kinetic Resolution of a Primary Amine by an Efficient Bifunctional Pd-CALB Hybrid Catalyst. A Metalloenzyme Mimic for Enhanced Cooperative Catalysis 503.4 Highly Efficient DKR of Secondary 1-Phenylethanol Derivatives Using a Low-Cost Solid Super Acid as Racemization Catalyst 533.5 Identification of New Biocatalysts for the Enantioselective Conversion of Tertiary Alcohols 583.6 Enzyme-Catalyzed Hydrolysis of Bicycloheptane Diester to Monoester 603.7 Double Mutant Lipase with Enhanced Activity and Enantioselectivity for Bulky Secondary Alcohols 643.8 Stereoselective Synthesis of β-Amino Acids by Hydrolysis of an Aryl-Substituted Dihydropyrimidine by Hydantoinases 68References 724 Non-Redox Lyases and Transferases for C-C, C-O, C-S, and C-N Bond Formation 754.1 Regioselective Enzymatic Carboxylation of Phenols and Hydroxystyrenes Employing Co-Factor-Independent Decarboxylases 754.2 Stetter Reactions Catalyzed by Thiamine Diphosphate-Dependent Enzymes 814.3 Asymmetric Michael-Type Additions of Acetaldehyde to Nitroolefins Catalyzed by 4-Oxalocrotonate Tautomerase (4-OT) Yielding Valuable γ-Nitroaldehydes 854.4 Michael-Type Addition of Aldehydes to β-Nitrostyrenes by Whole Cells of Escherichia coli Expressing 4-Oxalocrotonate Tautomerase (4-OT) 914.5 Norcoclaurine Synthases for the Biocatalytic Synthesis of Tetrahydroisoquinolines 954.6 Streptavidin-Based Artificial Metallo-Annulase for the Enantioselective Synthesis of Dihydroisoquinolones 1014.7 Regiospecific Benzylation of Tryptophan and Derivatives Catalyzed by a Fungal Dimethylallyl Transferase 1024.8 Enantioselective Michael Addition of Water Using Rhodococcus Rhodochrous ATCC 17895 1064.9 Sulfation of Various Compounds by an Arylsulfotransferase from Desulfitobacterium hafniense and Synthesis of 17β-Estradiol-3-Sulfate 1114.10 Asymmetric Synthesis of Cyclopropanes and Benzosultams via Enzyme-Catalyzed Carbenoid and Nitrenoid Transfer in E. coli Whole Cells 1134.11 Biocatalytic Production of Novel Glycolipids 1184.12 Enzymatic Synthesis of 8-Aza- and 8-Aza-7-Deazapurine 2´-Deoxyribonucleosides 1244.13 Phenylalanine Ammonia Lyase-Catalyzed Asymmetric Hydroamination for the Synthesis of L-Amino Acids 128References 1305 Oxidations 1355.1 Semi-Preparative-Scale Drug Metabolite Synthesis with Human Flavin Monooxygenases 1355.2 Biobased Synthesis of Industrially Relevant Nitriles by Selective Oxidative Decarboxylation of Amino Acids by Vanadium Chloroperoxidase 1395.3 Terminal Oxygenation of Fatty Acids by a CYP153A Fusion Construct Heterologously Expressed in E. coli 1425.4 Enantioselective Oxidative C-C Bond Formation in Isoquinoline Alkaloids Employing the Berberine Bridge Enzyme 1445.5 Oxidation of Aldehydes Using Alcohol Dehydrogenases 1485.6 MAO-Catalyzed Deracemization of Racemic Amines for the Synthesis of Pharmaceutical Building Blocks 1505.7 Synthesis of (S)-Amines by Chemo-Enzymatic Deracemization Using an (R)-Selective Amine Oxidase 1535.8 Selective Oxidation of Diols into Lactones under Aerobic Conditions Using a Laccase-TEMPO Catalytic System in Aqueous Medium 156References 1606 Reductions 1636.1 Tetrahydroxynaphthalene Reductase: Broad Substrate Range of an NADPH-Dependent Oxidoreductase Involved in Reductive Asymmetric Naphthol Dearomatization 1636.2 Chemoenzymatic Synthesis of Diastereo- and Enantiomerically Pure 2,6-Disubstituted Piperidines via Regioselective Monoamination of 1,5-Diketones 1676.3 Asymmetric Amination of Ketones Employing ω-TAs in Organic Solvents 1716.4 Stereoselective Synthesis of (R)-Profen Derivatives by the Enoate Reductase YqjM 1766.5 Productivity Improvement of the Bioreduction of α,β-Unsaturated Aldehydes by Coupling of the In Situ Substrate Feeding Product Removal (SFPR) Strategy with Isolated Enzymes 1816.6 Reduction of Imines by Recombinant Whole-Cell E. coli Biocatalysts Expressing Imine Reductases (IREDs) 186References 1917 Halogenation and Dehalogenation 1937.1 Site-Directed Mutagenesis Changes the Regioselectivity of the Tryptophan 7-Halogenase PrnA 1937.2 Controlling Enantioselectivity of Halohydrin Dehalogenase from Arthrobacter sp. Strain AD2, Revealed by Structure-Guided Directed Evolution 1977.3 Enzymatic Production of Chlorothymol and its Derivatives by Halogenation of the Phenolic Monoterpenes Thymol and Carvacrol with Chloroperoxidase 2017.4 Halogenation of Non-Activated Fatty Acyl Groups by a Trifunctional Non-Heme Fe(II)-Dependent Halogenase 204References 2118 Cascade Reactions 2138.1 Synthetic Cascades via a Combination of Artificial Metalloenzymes with Monoamine Oxidases (MAO-Ns) 2138.2 Amination of Primary Alcohols via a Redox-Neutral Biocascade 2158.3 Biocatalytic Synthesis of a Diketobornane as a Building Block for Bifunctional Camphor Derivatives 2188.4 Three Enzyme-Catalyzed Redox Cascade for the Production of a Carvo-Lactone 2228.5 Preparation of Homoallylic Alcohols via a Chemoenzymatic One-Pot Oxidation-Allylation Cascade 2268.6 Cascade Biotransformations via Enantioselective Reduction, Oxidation, and Hydrolysis: Preparation of (R)-δ-Lactones from 2-Alkylidenecyclopentanones 2308.7 One-Pot Tandem Enzymatic Reactions for Efficient Biocatalytic Synthesis of D-Fructose-6-Phosphate and Analogs 2328.8 Efficient One-Pot Tandem Biocatalytic Process for a Valuable Phosphorylated C8 D-Ketose: D-Glycero-D-Altro-2-Octulose 8-Phosphate 2398.9 Chemoenzymatic Synthesis of (S)-1,2,3,4-Tetrahydroisoquinoline-3-Carboxylic Acid by PAL-Mediated Amination and Pictet-Spengler Cyclization 2438.10 ω-TA/MAO Cascade for the Regio- and Stereoselective Synthesis of Chiral 2,5-Disubstituted Pyrrolidines 246References 2499 Biocatalysis for Industrial Process Development 2539.1 Efficient Synthesis of (S)-1-(5-Fluoropyrimidin-2-yl)ethylamine Hydrochloride Salt Using an ω-Transaminase Biocatalyst in a Two-Phase System 2539.2 Preparative-scale Production of a Chiral, Bicyclic Proline Analog Intermediate for Boceprevir 2579.3 Focused Carbonyl Reductase Screening for Rapid Gram Supply of Highly Enantioenriched Secondary Alcohol Libraries 2609.4 A Rapid, Inexpensive and Colorimetric High-throughput Assay Format for Screening Commercial Ketoreductase Panels, Providing Indication of Substrate Scope, Co-factor Specificity and Enantioselectivity 2669.5 Stereoselective Production of (R)-3-quinuclidinol Using Recombinant Escherichia coli Whole Cells Overexpressing 3-Quinuclidinone Reductase and a Co-factor Regeneration System 2739.6 Preparation of N-Boc-D-Serine Using a Coupled D-Acylase/Racemase Enzyme System 2759.7 Scale-up of a Biocatalytic Oxidase in a Dynamically Mixed Tubular Flow Reactor 279References 282Index 285