Enzyme-Based Organic Synthesis

Preface Acknowledgements Chapter 01 Introduction 1.1 Discovery and nature of enzyme 1.2 Enzyme structure and catalytic function 1.2.1 Enzyme structure 1.2.2 Catalytic function 1.3 Cofactors and coenzymes 1.4 Molecular recognition and enzyme specificity 1.4.1 Substrate specificity 1.4.2 Regiospecificity 1.4.3 Stereo-specificity 1.5 Enzyme classes and nomenclature 1.6 Enzyme and green chemistry Chapter 02 Organic Synthesis with Oxidoreductases 2.1 Oxidation reactions 2.1.1 Oxidation of alcohols and aldehydes 2.1.2 Hydroxylation of alkanes 2.1.3 Hydroxylation of aromatic compounds 2.1.4 Dihydroxylation of aromatic compounds 2.1.5 Epoxidation 2.1.6 Sulfoxidation reactions 2.1.7 Baeyer-Villiger reactions 2.1.8 Peroxidation reactions 2.2 Reduction reactions 2.2.1 Reduction of aldehydes and ketones 2.2.2 Reduction of C=C bonds Bibliography Chapter 3 Organic Synthesis with Transferases 3.1 Transamination with Aminotransferases 3.2 Glycosyl-transfer with glycosyltransferase 3.3 Phosphorylation with kinases 3.4 Acetyl group transfer with acetyltransferase Bibliography Chapter 4 Organic Synthesis with Hydrolases 4.1 Hydrolysis of ester bond 4.1.1 Ester hydrolysis with esterases 4.1.2 Ester hydrolysis with lipases 4.1.3 Ester hydrolysis with proteases 4.2 Hydrolysis of amide bond 4.3 Hydrolysis of phosphate esters 4.4 Hydrolysis of epoxides 4.5 Hydrolysis of hydantoins 4.6 Hydrolysis of glycosidic bonds and natural polysaccharides 4.6.1 Hydrolysis of starch and applications 4.6.2 Hydrolysis of cellulose and applications 4.6.3 Hydrolysis of hemicellulose and applications Bibliography Chapter 5 Organic Synthesis with Lyases 5.1 Lyases with carbon-carbon bonds 5.1.1 Aldolases in organic syntheses 5.1.2 Enzymatic acyloin condensation 5.1.2.1 Acyloin condensation catalyzed by pyruvate decarboxylase 5.1.2.2 Acyloin condensation catalyzed by benzoylformate decarboxylase 5.1.2.3 Acyloin condensation catalyzed by benzaldehyde lyase 5.1.2.4 Acyloin condensation catalyzed by phenylpyruvate decarboxylase 5.1.3 Cyanohydrin formation with hydroxynitrile lyases 5.2 Lyases with carbon-oxygen bonds 5.2.1 Enzyme-catalyzed water addition to electron-rich C=C bonds 5.2.1.1 Oleate hydratase 5.2.1.2 Linalool dehydratase-isomerase 5.2.1.3 Limonene hydratase 5.2.2 Enzyme-catalyzed water addition to electron-deficient C=C bonds 5.2.2.1 Fumarase 5.2.2.2 Malease 5.2.2.3 Enoyl-CoA hydratase 5.3 Lyases with carbon-nitrogen bonds 5.3.1 Aspartate ammonia lyase 5.3.2 Methylaspartate ammonia lyase 5.3.3 Aromatic amino acid ammonia lyases 5.3.3.1 L-Arylalanines synthesis 5.3.3.2 D-Arylalanines synthesis 5.3.3.3 b-Arylalanines synthesis 5.3.3.4 Applications for arylalanines synthesis 5.4 Lyases with carbon-sulfur bonds 5.5 Lyases with carbon-halide bonds 5.5.1 Synthesis of chiral epoxides 5.5.2 Synthesis of enantiopure ß-substituted alcohols 5.5.3 Application of cascade reactions Bibliography Chapter 6 Organic Synthesis with Isomerases 6.1 Amino acid racemases not requiring cofactors 6.2 Amino acid racemases requiring pyridoxal 5'-phosphate 6.3 Mandelate racemase 6.4 Isopenicillin N epimerase 6.5 Aldose-ketose isomerases 6.6 L-Rhamnose isomerase 6.7 L-fucose isomerase 6.8 N-Acetyl-D-glucosamine 2- epimerase 6.9 Allylic isomeriation 6.10 Maleylacetoacetate isomerase 6.11 Retinol isomerase 6.12 Maleate cis-trans isomerase 6.13 Unsaturated fatty acid cis-trans isomerase Bibliography Chapter 7 Organic Synthesis with Ligases 7.1 Aldol reactions with aldolases 7.2 Keto and aldol transfer reactions with transketolase 7.3 Dehydroquinate synthase 7.4 Thiolase 7.5 Isoprenoid synthesis Bibliography Chapter 8 Future Perspectives 8.1 Monooxygenation and dioxygenation 8.2 Substitutions 8.3 Formylation, hydroxymethylation, methylation 8.4 Rearrangements Bibliography Index