Wolf-D. Woggon is Emeritus Professor of Organic Chemistry in the Department of Chemistry at the University of Basel (Switzerland). He completed his PhD in organic chemistry at the University of Zurich (Switzerland) with the late Hans Schmid. After a postdoctoral stay with Alan Battersby in Cambridge (UK), he started his independent research at the University of Zurich and completed his habilitation in 1985. In 1995, he became professor at the University of Basel. His research interests include the synthesis of enzyme models, enzymatic reaction mechanisms, isolation of new enzymes, the synthesis of vitamins, metalloporphyrins, cyclodextrins and the development of new ligand-scaffolds for metal-organic catalysis. He has served for six years as head of the Department of Chemistry at the University of Basel and for further four years as its managing director.

Preface vii

1 Enzymatic C¿C Bond Formation by Aldol Reactions 1

Aldolases 1

Class I Aldolases 1

Bioorganic Class I Aldolase Reactions 3

Class II Aldolases 9

Class II Aldolase Mimics 11

References 13

2 Fatty Acid- and Polyketide-Synthases - Claisen-Type C¿C Bond Formation 15

Biomimetic Decarboxylative C¿C Bond Formation 20

References 23

3 Carbenium-Ion-Driven C¿C Bond Formations - Terpenes 25

Enzyme-like Cyclisations Involving Carbenium Ions 30

References 41

4 Oxidations Catalysed by Heme Complexes 43

Monooxygenases 43

Cytochromes P 450 45

Synthetic P450 Enzyme Models 51

Chloroperoxidase (CPO) 57

Synthetic Enzyme Mimics of Chloroperoxidase (CPO) 60

NO Synthase (NOS) 63

References 67

5 Oxidations Catalysed by Non-heme Complexes and Other Co-factors 69

Methane Monooxygenase 69

Active Site Analogues of Methane Monooxygenase 71

Enzyme Mimics of Cu Monooxygenases 75

Flavin-dependent Monooxygenases 78

Enzyme Mimics of Baeyer-Villiger Monooxygenases 83

References 95

6 C-H Activation 97

References 110

7 Dioxygenases 111

Metal Complexes Displaying Dioxygenase-like Reactivity 127

References 134

8 Oxidoreductases 137

Cytochrome c Oxidase 148

References 150

9 Synthetic Systems That Mimic Certain Aspects of Oxidoreductases 153

References 173

Index 175