Enzymes in Synthetic Organic Chemistry

Preface. Acknowledgements. General Aspects. Rate acceleration in enzyme-catalyzed reactions. Michaelis-Menten kinetics. Enzyme inhibition. Specificity. Improvement or alteration of enzyme specifity. Enzyme stabilization and reactor configuration. Cofactor regeneration. Enzyme catalysis in organic solvents. Multienzyme systems and metabolic engineering. Rational design of new enzymatic catalysts. Conclusion. References. Use of Hydrolytic Enzymes: Amidases, Proteases, Esterases, Lipases, Nitrilases, Phosphatases, Epoxide Hydrolases. Amidases. Protease-catalyzed peptide synthesis. Proteases that act as esterases. Acetylcholine esterase. Pig liver esterase. Phospholipases. Cholesterol esterase. Lipases. Nitrile hydrolysis enzymes. Epoxide hydrolase. Phosphatase. References. Oxidoreductions. Nicotinamide cofactor dependent oxidoreductions. Dehydrogenases which utilize ketoacids as substrates. Other NAD(P)-dependent dehydrogenases. Oxidoreductases that are metalloenzymes. References. C-C Bond Formation. Aldol condensation. Ketol and aldol transfer reaction. Addition of HCN to aldehydes. Acyloin condensation. C-C bond forming reactions involving acetyl coA. Isoprenoid and steroid synthesis. &bgr;-replacement of chloroalanine. C-C bond formation catalyzed by vitamin B12. References. Synthesis of Glycoside Bonds. Background. Glycosyltransferases of the Leloir pathway. Substrate specificity and synthetic applications of glycosyltransferases. Non-Leloir glycosyltransferases. Glycosidases. Transglycosidases. Synthesis of N-glycosides. Biological applications of synthetic glycoconjugates. Future opportunities. References. Addition, Elimination and Other Group Transfer Reactions (Phosphoryl-, Methyl-, Sulpho- and Amino-Transfer Reactions). Addition of water to alkenes: fumarase. Addition of ammonia to double bonds: ammonia lyases. Transamination: aminotransferases. Addition and elimination of carboxyl group. Nucleoside triphosphate requiring enzymatic reactions. Preparation of ATP chiral at &agr;-, &bgr;- or &ggr;-phosphorous. Phosphorothioate-containing DNA and RNA. DNA and RNA oligomers. Incorporation of modified or unnatural bases into DNA or RNA. Dehalogenation. Synthesis of chiral methyl groups. S-Adenosylmethionine and transmethylation. Sulfate activation and transfer reactions. References. Subject index.