Biotransformations in Organic Chemistry

1        Introduction and Background Information1.1 Introduction..........................................................................................1.2 Common Prejudices Against Enzymes...............................................1.3 Advantages and Disadvantages of Biocatalysts..................................1.3.1 Advantages of Biocatalysts........................................................1.3.2 Disadvantages of Biocatalysts...................................................1.3.3 Isolated Enzymes Versus Whole Cell Systems.........................1.4 Enzyme Properties and Nomenclature...............................................1.4.1 Structural Biology in a Nutshell..............................1.4.2 Mechanistic Aspects of Enzyme Catalysis...........................1.4.3 Classification and Nomenclature............................................1.4.4 Coenzymes.......................................................................1.4.5 Enzyme Sources..............................................................References..... ................................................................................... 2 Biocatalytic Applications 2.1 Hydrolytic Reactions..........................................................................2.1.1 Mechanistic and Kinetic Aspects.............................................2.1.2 Hydrolysis of the Amide Bond................................................2.1.3 Ester Hydrolysis.......................................................................2.1.3.1       Esterases and Proteases.............................................2.1.3.2       Lipases.......................................................................2.1.4 Hydrolysis and Formation of Phosphate Esters......................2.1.5 Hydrolysis of Epoxides...........................................................2.1.6 Hydrolysis of Nitriles..............................................................References........................................................................................2.2 Reduction Reactions..........................................................................2.2.1 Recycling of Cofactors............................................................2.2.2           Reduction of Aldehydes and Ketones Using Isolated Enzymes...................................................................2.2.3 Reduction of Aldehydes and Ketones Using Whole Cells....2.2.4 Reduction of C=C-Bonds .......................References........................................................................................2.3 Oxidation Reactions..........................................................................2.3.1 Oxidation of Alcohols and Aldehydes...................................2.3.2 Oxygenation Reactions...........................................................2.3.2.1       Hydroxylation of Alkanes........................................2.3.2.2       Hydroxylation of Aromatic Compounds.................2.3.2.3       Epoxidation of Alkenes............................................2.3.2.4       Sulfoxidation Reactions............................................2.3.2.5       Baeyer-Villiger Reactions.........................................2.3.2.6       Formation of Peroxides.............................................2.3.2.7       Dihydroxylation of Aromatic Compounds...............2.3.3 Peroxidation Reactions............................................................References.... ...................................................................................2.4 Formation of Carbon-Carbon Bonds.................................................2.4.1 Aldol Reactions.......................................................................2.4.2 Thiamine-Dependent Acyloin- and Benzoin Reactions.........2.4.3 Michael-Type Additions.........................................................References........................................................................................2.5 Addition and Elimination Reactions.................................................2.5.1 Cyanohydrin Formation..........................................................2.5.2 Addition of Water...........................................2.5.3 Addition of Ammonia...........................................References........................................................................................2.6 Transfer Reactions.............................................................2.6.1 Glycosyl Transfer Transferases..............................................2.6.1.1       Glycosyl Transferases........................................2.6.1.2       Glycosidases........................................2.6.2 Amino Transfer Reactions...................................................References........................................................................................2.7 Halogenation and Dehalogenation Reactions...................................2.7.1 Halogenation...........................................................................2.7.2 Dehalogenation.......................................................................References....................................................................................... 3        Special Techniques 3.1 Enzymes in Organic Solvents..........................................................3.1.1 Ester Synthesis........................................................................3.1.2 Lactone Synthesis...................................................................3.1.3 Amide Synthesis.....................................................................3.1.4 Peptide Synthesis....................................................................3.1.5 Peracid Synthesis....................................................................3.1.6 Redox Reactions.....................................................................3.1.7 Medium Engineering...............................................................3.2 Immobilization..................................................................................3.3 Artificial and Modified Enzymes.....................................................3.3.1 Artificial Enzyme Mimics.....................................................3.3.2 Modified Enzymes..........................................................3.3.2.1       Chemically Modified Enzymes................................3.3.2.2       Genetically Modified Enzymes................................3.3.3 Catalytic Antibodies................................................................References........................................................................................ 4        State of the Art and Outlook................................................................. 5        Appendix 5.1 Basic Rules for Handling Biocatalysts..............................................5.2 Abbreviations....................................................................................5.3 Suppliers of Enzymes.......................................................................5.4 Commonly Used Enzyme Preparations...........................................5.5 Major Culture Collections................................................................5.6 Pathogenic Bacteria and Fungi........................................................