Contents

Preface xi

Part 1 Novel reaction conditions for biotransformation 1 CHAPTER 1

Biotransformation in ionic liquid 3

Toshiyuki Itoh

1. Introduction 3

2. Ionic Liquids as a Reaction Medium for Biotransformation 3

3. Lipase-Catalyzed Reaction in an Ionic Liquid Solvent System 7

4. Activation of Lipase by an Ionic Liquid 10

5. Various Biotransformations in an Ionic Liquid Solvent System 15

6. Concluding Remarks 18 References 18

CHAPTER 2

Temperature control of the enantioselectivity in the lipase-catalyzed resolutions 21

Takashi Sakai

1. Introduction 21

2. Finding of the "Low-Temperature Method" in the Lipase-Catalyzed Kinetic Resolution 22

3. Theory of Temperature Effect on the Enantioselectivity 23

4. General Applicability of the "Low-Temperature Method" Examined 28

4.1. Application to solketal and other primary and secondary alcohols 28

4.2. Resolution of (±)-2-hydroxy-2-(pentafluorophenyl)acetonitrile 30

4.3. Immobilization of lipase on porous ceramic support (Toyonite) for acceleration 31

4.4. Structural optimization of organic bridges on Toyonite 32

4.5. Practical resolution of azirine 1 by the "low-temperature method" combined with Toyonite-immobilized lipase and optimized acylating agent 33

4.6. Resolution of (2R*, 3S*)- and (2R*, 3R*)-3-methyl-3-phenyl-2-aziridinemethanols 34

4.7. Resolution of 5-(hydroxymethyl)-3-phenyl-2-isoxazoline 36

4.8. Application of temperature control to asymmetric protonation 37

4.9. Lipase-catalyzed resolutions at high temperatures up to 120°C 37

5. Low-Temperature Reactions in Literatures 37

6. Lipase-Catalyzed Resolution of Primary Alcohols: Promising Candidates for the "Low-Temperature Method" 40

7. Conclusion 45 References 45

CHAPTER 3

Future directions in photosynthetic organisms-catalyzed reactions 51

Kaoru Nakamura

1. Introduction 51

2. Reduction Reaction 51

3. Oxidation and Hydroxylation 55

4. Removal of Organic and Inorganic Substances in Wastewater 56

5. Conclusion 57 References 57

CHAPTER 4

Catalysis by enzyme-metal combinations 59

Mahn-Joo Kim, Jaiwook Park, Yangsoo Ahn, Palakodety R. Krishna

1. Introduction 59

2. Dynamic Kinetic Resolutions by Enzyme-Metal Combinations 60 2.1. DKR of secondary alcohols 60

3. Asymmetric Transformations by Enzyme-Metal Combinations 73

3.1. Asymmetric transformation of ketone 73

3.2. Asymmetric transformation of enol ester 75

3.3. Asymmetric transformation of ketoxime 76

4. Conclusion 78 Acknowledgements 78 References 79

Part 2 Uncomon kind of biocatalytic reaction 81 CHAPTER 5

Biological Kolbe-Schmitt carboxylation 83 Possible use of enzymes for the direct carboxylation of organic substrates

Toyokazu Yoshida, Toru Nagasawa

1. Introduction 83

2. Enzymes Catalyzing the Carboxylation of Phenolic Compounds 84

2.1. 4-Hydroxybenzoate decarboxylase (EC 4.1.1.61) 85

2.2. 3,4-Dihydroxybenzoate decarboxylase (EC 4.1.1.63) 87

2.3. Phenolphosphate carboxylase (EC 4.1.1.-) in Thauera aromatica 88

2.4. 2,6-Dihydroxybenzoate decarboxylase 91

2.5. 2,3-Dihydroxybenzoate decarboxylase 95

3. Enzymes Catalyzing the Direct Carboxylation of Heterocyclic Compounds 95

3.1. Pyrrole-2-carboxylate decarboxylase 96

3.2. Indole-3-carboxylate decarboxylase 99

4. Structure Analysis of Decarboxylases Catalyzing CO2 Fixation 101

4.1. Class I decarboxylases 102

4.2. Class II decarboxylases 103

4.3. Phenylphosphate carboxylase 103

5. Conclusion 103 References 104

CHAPTER 6

Discovery, redesign and applications of Baeyer-Villiger monooxygenases 107

Daniel E. Torres Pazmino, Marco W. Fraaije

1. Introduction 107

2. Biocatalytic Properties of Recombinant Available BVMOs 110

2.1. Discovery of novel BVMOs 112

2.2. Exploring sequenced (meta)genomes for novel BVMOs 114

2.3. Screening the metagenome for novel BVMOs 118

2.4. Redesign of BVMOs 119

3. Conclusions: Future Directions 122 References 125

CHAPTER 7

Enzymes in aldoxime-nitrile pathway: versatile tools in biocatalysis 129

Yasuhisa Asano

1. Introduction 129

2. Screening for New Microbial Enzymes by Enrichment and Acclimation

Culture Techniques 129

3. Development of Nitrile-Degrading Enzymes 131

4. Screening for Heat-Stable NHase 131

5. Screening for NHase with PCR 132

6. Nitrile Synthesis Using a New Enzyme, Aldoxime Dehydratase 133

6.1. Aldoxime-converting enzymes 133

6.2. Isolation of microorganisms having aldoxime dehydratase activity 134

6.3. Purification, characterization and primary structure determination of aldoxime dehydratase 134

6.4. Synthesis of nitriles from aldoxime with aldoxime dehydratase 135

6.5. Distribution of aldoxime dehydratase 136

6.6. Molecular screening for "aldoxime-nitrile pathway" 136

7. Conclusions 137 Acknowledgments 137 References 137

CHAPTER 8

Addition of hydrocyanic acid to carbonyl compounds 141

Franz Effenberger, Anja Bohrer, Siegfried Forster

1. Introduction 141

2. Optimized Reaction Conditions for the HNL-Catalyzed Formation of Chiral Cyanohydrins 143

3. Synthetic Potential of Chiral Cyanohydrins in Stereoselective Synthesis 145

3.1. Chiral 2-hydroxy carboxylic acids 145

3.2. Optically active 1,2-amino alcohols 147

3.3. Stereoselective substitution of the hydroxyl group in chiral cyanohydrins 148

3.4. Stereoselective synthesis of substituted cyclohexanone cyanohydrins 149

4. Crystal Structures of Hydroxynitrile Lyases and Mechanism of Cyanogenesis 149

4.1. Crystal structures of HNLs 151

4.2. Reaction mechanism of cyanogenesis 151

4.3. Changing substrate specificity and stereoselectivity applying Trp128 mutants of wt-MeHNL 152

5. Conclusions 153 References 154

Part 3 Novel compounds synthesized by biotransformations 157 CHAPTER 9

Chiral heteroatom-containing compounds 159

Piotr Kietbasifiski, Marian Mikolajczyk

1. Introduction 159

2. Organosulfur Compounds 160

2.1. C-chiral hydroxy sulfides and derivatives 160

2.2. C-chiral hydroxyalkyl sulfones 163

2.3. C-chiral alkyl sulfates 165

2.4. Other C-chiral organosulfur compounds 166

2.5. S-chiral sulfinylcarboxylates 166

2.6. S-chiral hydroxy sulfoxides 168

2.7. S-chiral sulfinamides 169

2.8. S-chiral sulfoximines 171

3. Organophosphorus Compounds 172

3.1. C-chiral hydroxy phosphorus derivatives 172

3.2. C-chiral amino phosphorus compounds 180

3.3. P-chiral phosphoro-acetates 183

3.4. P-chiral hydroxy phosphoryl compounds 186

3.5. P-chiral hydroxy phosphorus P-boranes 191

3.6. Stereocontrolled transformations of organophosphorus acid esters 192

4. Organosilanes 196

5. Organogermanes 197

6. Future Perspectives 197 References 199

CHAPTER 10

Enzymatic polymerization 205

Hiroshi Uyama

1. Introduction 205

2. Enzymatic Synthesis of Polyesters 206

2.1. Ring-opening polymerization to polyesters 207

2.2. Polycondensation of dicarboxylic acid derivatives and glycols to polyesters 212

2.3. Enzymatic synthesis of functional polyesters 219

3. Enzymatic Synthesis of Phenolic Polymers 228

3.1. Enzymatic oxidative polymerization of phenols 228

3.2. Enzymatic synthesis of functional phenolic polymers 233

3.3. Artificial urushi 238

3.4. Enzymatic synthesis and biological properties of flavonoid polymers 240 4. Concluding Remarks 244 References 245

CHAPTER 11

Synthesis of naturally occurring ß-D-glucopyranosides based on enzymatic ß-glucosidation using ß-glucosidase from almond 253

Hiroyuki Akita

1. Introduction 253

2. Synthesis of ß-D-Olucopyranoside Under Kinetically Controlled Condition 255 2.1. Synthesis of naturally occurring ß-D-glucopyranoside 259

3. Synthesis of ß-D-Olucopyranoside Under Equilibrium-Controlled Condition 262

3.1. Immobilization of ß-D-glucosidase using prepolymer 263

3.2. Enzymatic transglucosidation 263

3.3. Synthesis of naturally occurring benzyl ß-D-glucopyranoside 267

3.4. Synthesis of phenethyl ß-D-glycopyranoside 270

3.5. Synthesis of (3Z)-hexenyl ß-D-glycopyranoside 272

3.6. Synthesis of geranyl ß-D-glycopyranoside 275

3.7. Synthesis of Sacranosides A (89) and B (90) 277

3.8. Synthesis of naturally occurring n-octyl ß-D-glucopyranosides 278

3.9. Synthesis of naturally occurring hexyl ß-D-glucopyranosides 280

3.10. Synthesis of naturally occurring phenylpropenoid ß-D-glucopyranoside 282

4. Future Aspect 287

5. Conclusion 289 References 289

Part 4 Use of molecular biology technique to find novel biocatalyst 291 CHAPTER 12

Future directions in alcohol dehydrogenase-catalyzed reactions 293

Jon D. Stewart

1. Introduction 293

2. Future Progress in the Discovery Phase of Dehydrogenases 295

2.1. Accurately predicting dehydrogenase structures 295

2.2. Predicting dehydrogenase substrate acceptance and stereoselectivities. 296

2.3. Rapid screening of novel dehydrogenases 296

2.4. Dehydrogenases for large substrates 299

2.5. Dehydrogenase modules within larger assemblies as monofunctional catalysts 299

2.6. Dehydrogenase catalysis of other 1,2-carbonyl additions 300

3. Future Progress in Dehydrogenase Process Development 300

3.1. Improving the kinetic properties of dehydrogenases 301

3.2. Reductions of highly hydrophobic substrates 301

3.3. Cofactorless dehydrogenases? 302

4. Conclusions 302 Acknowledgments 303 References 303

CHAPTER 13

Enzymatic decarboxylation of synthetic compounds 305

Kenji Miyamoto, Hiromichi Ohta

1. Introduction 305

2. Arylmalonate Decarboxylase 309

2.1. Discovery of arylmalonate decarboxylase and its substrate specificity 310

2.2. Purification of the enzyme and cloning of the gene 311

2.3. Reaction mechanism 312

2.4. Inversion of enantioselectivity based on the reaction mechanism and homology 317

2.5. Addition of racemase activity 319

3. Transketolase-Catalyzed Reaction 321

3.1. Substrate specificity and stereochemical source of TKase-catalyzed reaction 322

3.2. Application of TKase-catalyzed reaction in organic syntheses 322

3.3. Tertiary structure and mutagenesis studies 329

4. Future Trends of this Area 331

4.1. Application of decarboxylation reaction to dialkylmalonates 331

4.2. Decarboxylation of various carboxylic acids 332

4.3. Oxidative decarboxylation of ^-hydroxycarboxylic acids 333

4.4. Carboxylation 336

4.5. Development of biotransformation via enolate 337

4.6. Utilization of database and informatics 339

5. Conclusion 339 References 340

Index

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