Practical Methods for Biocatalysis and Biotransformations 2

John Whittall, Manchester Interdisciplinary Biocentre, Manchester University, UK. Peter W Sutton, GlaxoSmithKline Research and Development Limited, UK.

• List of Contributors ixAbbreviations xxiii1 Biocatalysis in the Fine Chemical and Pharmaceutical Industries 11.1 Introduction 11.2 Biotrans Outsourcing – AstraZeneca 41.3 Biotrans Trends – Lonza 51.4 Biocatalysis in the Pharma Environment 91.5 Industrial Use of Hydrolases 241.6 Industrial Biooxidation and Reduction 321.7 Industrial Application of Transaminases – Cambrex 361.8 Biocatalyst Discovery and Improvement 381.9 From Pathway Engineering to Synthetic Biology 421.10 Prioritization of Future Biocatalysis and Synthetic Biology Needs 471.11 Concluding Remarks 522 Reductive Amination 612.1 o-Transaminases – Useful Biocatalysts for Chiral Amine Synthesis 612.2 Preparative Scale Production of a Bulky–Bulky Chiral Amine Using an Engineered Transaminase 642.3 Synthesis of Optically Pure Amines Employing o-Transaminases 692.4 A Fast, Sensitive Assay and Scale-Up of o-Transaminase Catalysed Reactions 742.5 Asymmetric Synthesis of L-3-Hydroxyadamantylglycine Using Branched Chain Aminotransferase 792.6 Asymmetric Reduction of Aryl Imines Using Candida parapsilosis ATCC 7330 833 Enoate Reductases for Reduction of Electron Deficient Alkenes 873.1 Asymmetric Bioreduction of Activated Alkenes Using Ene-Reductases from the Old Yellow Enzyme Family 873.2 Efficient Baker's Yeast Mediated Reduction with Substrate Feeding Product Removal (SFPR) Technology: Synthesis of (S)-2-Alkoxy-3-Aryl-1-Propanols 963.3 Asymmetric Reduction of (4S)-(+)-Carvone Catalyzed by Enoate Reductases (ERs) Expressed by Non-Conventional Yeast (NCY) Whole Cells 1003.4 Preparation of Enantiomerically Pure Citronellal Enantiomers Using Alkene Reductases 1043.5 Highly Enantiomeric Hydrogenation of C–C Double Bond of Methylated N-Phenyl and N-Phenylalkylmaleimides by Aspergillus fumigatus 1084 Industrial Carbonyl Reduction 1154.1 Bioreduction Using Immobilized Carbonyl Reductase Technology 1164.2 Preparative Ketoreductase-Catalyzed Kinetic Resolution of a Racemic Aldehyde 1184.3 Enzymatic Reduction of 2,6-dichloro-3-fluoro-acetophenone to Produce (S)-1-(2,6-dichloro-3-fluorophenyl)ethanol 1214.4 Preparative Scale Production of Poorly Soluble Chiral Alcohol Intermediate for Montelukast 1245 Regio- and Stereoselective Hydroxylation 1295.1 Engineering of an Amycolatopsis orientalis P450 Compactin Hydroxylase into a Pravastatin Synthase by Changing the Stereospecificity of the Enzyme 1305.2 Recombinant Human Cytochrome P450 Enzymes Expressed in Escherichia coli as Whole Cell Biocatalysts: Preparative Synthesis of Oxidized Metabolites of an mGlu5 Receptor Antagonist 1385.3 Alpha-Keto Biooxidation Using Cunninghamella echinulata (DSM 63356) 1475.4 Aromatic Hydroxylation: Preparation of 3,4-Dihydroxyphenylacetic Acid 1505.5 Regioselective Aromatic Hydroxylation of Quinaldine Using Living Pseudomonas putida Cells Containing Quinaldine 4-Oxidase 1535.6 Regioselective Preparation of 5-Hydroxypropranolol with a Fungal Peroxygenase 1585.7 Microbial Conversion of b-Myrcene to Geraniol by a Strain of Rhodococcus 1596 Oxidation of Alcohols 1636.1 Preparative Method for the Enzymatic Synthesis of 5-Ketogluconic Acid and its Isolation 1636.2 Selective Enzymatic Oxidation of Atropisomeric Diaryl Ethers by Oxidation with Oxygen and Catalytic Galactose Oxidase M3–5 1666.3 Kinetic Resolution of Chiral Secondary Alcohols by Oxidation with Oxygen and Catalytic Galactose Oxidase M3-5 1696.4 ADH Catalyzed Oxidation of Sec-Alcohols Using Molecular Oxygen 1726.5 Irreversible Non-Enantioselective Oxidation of Secondary Alcohols Using Sphingobium ADH and Chloroacetone as Oxidant 1756.6 Chemoselective Oxidation of Primary Alcohols to Aldehydes 1777 Selective Oxidation 1817.1 Enantioselective Biocatalytic Oxidative Desymmetrization of Substituted Pyrrolidines 1827.2 Large Scale Baeyer–Villiger Monooxygenase-Catalyzed Conversion of (R,S)-3-phenylbutan-2-one 1867.3 Synthesis of Optically Active 3-Alkyl-3-,4-dihydroioscoumarins by Dynamic Kinetic Resolutions Catalyzed by a Baeyer–Villiger Monooxygenase 1907.4 Oxidative Cleavage of the B-Ring of (+)-Catechin 1937.5 18O-Isotopic Labeling in the Meta-Dioxygenase Cleavage of (þ)-Catechin B-Ring 1967.6 Biocatalytic Cleavage of Alkenes with Oxygen and Trametes hirsuta G FCC047 1998 Industrial Hydrolases and Related Enzymes 2038.1 Dynamic Kinetic Resolution of a-Halo Esters with Hydrolytic Enzymes and Sec-amine Bases 2038.2 Kinetic Resolution of an Amino Ester Using Supported Mucor miehei Lipase (Lipozyme RM IM) 2078.3 Large Scale Synthesis of (S)-Allysine Ethylene Acetal via Amino Acylase Resolution 2128.4 Pilot-Scale Synthesis of (1R,2S,4S)-7-Oxabicyclo[2.2.1] heptan-2-exo-carboxylic Acid 2148.5 A Selective Lipase-Catalyzed Mono-Acetylation of a Diol Suitable for a Telescoped Synthetic Process 2178.6 A Protease-Mediated Hydrolytic Kinetic Resolution of an Atropisomeric Ester Operating Within an Unusually Narrow pH Window 2208.7 Asymmetric Synthesis of Quaternary Amino Acids from Simple Bis Nitriles Using a Dual Nitrile Hydratase/Amidase Biocatalyzed Reaction 2238.8 Development of an Improved Immobilized CAL-B for the Enzymatic Resolution of a Key Intermediate to Odanacatib 2279 Transferases for Alkylation, Glycosylation and Phosphorylation 2319.1 Industrial Production of Caffeic Acid-a-D-O-Glucoside 2329.2 Enzymatic Synthesis of 5-Methyluridine by Transglycosylation of Guanosine and Thymine 2359.3 Preparation and Use of Sucrose Phosphorylase as Cross-Linked Enzyme Aggregate (CLEA) 2409.4 Enzymatic Synthesis of Phosphorylated Carbohydrates and Alcohols 2449.5 Biocatalyzed Synthesis of Chiral O-Phosphorylated Derivative of 2-Hydroxy-2-phenylethanephosphonate 2479.6 High Activity b-Galactosidase Preparation for Diastereoselective Synthesis of (R)-(1-Phenylethyl)-b-D-Galactopyranoside by Reverse Hydrolysis 2509.7 Stereospecific Synthesis of Aszonalenins by Using Two Recombinant Prenyltransferases 2549.8 Enzymatic Friedel–Crafts Alkylation Catalyzed by S-Adenosyl-L-methionine Dependent Methyl Transferase 25810 C–C Bond Formation and Decarboxylation 26310.1 Enzymatic, Stereoselective Synthesis of (S)-Norcoclaurine 26410.2 Preparation of Non-Natural Tyrosine Derivatives from Pyruvate and Phenol Derivatives 26710.3 Enzymatic a-Decarboxylation of L-Glutamic Acid in the Production of Biobased Chemicals 26910.4 Asymmetric Decarboxylation of Arylmalonates and Racemization of Profens by Arylmalonate Decarboxylase and its Variants 27410.5 Improved Enzymatic Preparation of 1-Deoxy-D-xylulose 5-Phosphate 28010.6 On the Use of 2-Methyltetrahydrofuran (2-MeTHF) as Bio-Based (Co-) Solvent in Biotransformations 28410.7 The Lipase-Catalyzed Asymmetric Michael Addition of Thienyl Nitroolefin to Acetylacetone 29111 Halogenation/Dehalogenation/Heteroatom Oxidation 29711.1 Preparation of Halogenated Molecules by a Fungal Flavin-Dependent Halogenase Heterologously Expressed in Escherichia coli 29911.2 Preparation of Optically Pure Haloalkanes and Alcohols by Kinetic Resolution Using Haloalkane Dehalogenases 30111.3 Preparation of Enantiopure Sulfoxides by Enantioselective Oxidation with Whole Cells of Rhodococcus sp. ECU0066 30711.4 Kinetic Resolution of an Insecticidal Dithiophosphate by Chloroperoxidase Catalyzed Oxidation of the Thiophosphoryl Group 31012 Tandem and Sequential Multi-Enzymatic Syntheses 31312.1 Production of Isorhamnetin 3-O-Glucoside in Escherichia coli Using Engineered Glycosyltransferase 31312.2 Multienzymatic Preparation of (-)-3-(Oxiran-2-yl)Benzoic Acid 31712.3 Enzymatic Synthesis of Carbohydrates from Dihydroxyacetone and Aldehydes by a One Pot Enzyme Cascade Reaction 32112.4 Aldolase Based Multi-Enzyme System for Carbon–Carbon Bond Formation 32312.5 Tandem Biocatalytic Process for the Kinetic Resolution of b-Phenylalanine and its Analogs 33112.6 A Chemoenzymatic Synthesis of a Deoxy Sugar Ester of N-Boc-Protected L-Tyrosine 33512.7 Electrochemical Systems for the Recovery of Succinic Acid from Fermentations 339Appendix 347Index 355

“In conclusion, the second volume of Practical Methods for Biocatalysis and Biotransformations is highly recommended, both to the nonspecialist in the area and to experts, too.”  (Organic Process Research & Development Journal, 1 April 2013)