Table of Contents

Contributors x

Preface xiii

1 Introduction: biochemistry; physiology and ecological functions of secondary metabolites Michael Wink 1

1.1 Introduction 1

1.2 Biosynthesis 2

1.3 Transport, storage and turnover 9

1.4 Costs of secondary metabolism 13

1.5 Ecological role of secondary metabolites 14

References 17

2 Biosynthesis of alkaloids and betalains Margaret F. Roberts Dieter Strack Michael Wink 20

2.1 Introduction 20

2.2 Nicotine and tropane alkaloids 23

2.3 Pyrrolizdine alkaloids (PAs) 33

2.4 Benzylisoquinoline alkaloids 35

2.5 Monoterpene indole alkaloids (MIA) 46

2.6 Ergot alkaloids 56

2.7 Acridone alkaloid biosynthesis 60

2.8 Purine alkaloids 61

2.9 Taxol 62

2.10 Betalains 66

2.11 Conclusions 75

References 75

3 Biosynthesis of cyanogenic glycosides, glucosinolates and non-protein amino acids Dirk Selmar 92

3.1 Introduction 93

3.2 Cyanogenic glycosides 94

3.3 Glucosinolates 128

3.4 Non-protein amino acids 146

Acknowledgements 157

References 157

4 Biosynthesis of phenylpropanoids and related compounds Maike Petersen Joachim Hans Ulrich Matern 182

4.1 Introduction 182

4.2 General phenylpropanoid pathway and formation of hydroxycinnamate conjugates 183

4.3 Coumarins 197

4.4 Lignans 209

4.5 Gallotannins and ellagitannins 223

4.6 Conclusion 229

References 230

5 Biochemistry of terpenoids: monoterpenes, sesquiterpenes and diterpenes Mohamed Ashour Michael Wink Jonathan Gershenzon 258

5.1 Introduction 259

5.2 Function 260

5.3 Biosynthesis 263

5.4 Conclusions 285

References 286

6 Biochemistry of sterols, cardiac glycosides, brassinosteroids, phytoecdysteroids and steroid saponins Wolfgang Kreis Frieder Müller-Uri 304

6.1 Introduction 305

6.2 Sterols 308

6.3 Cardiac glycosides 319

6.4 Brassinosteroids 336

6.5 Phytoecdysteroids 341

6.6 Steroid saponins and steroid alkaloids 343

6.7 Conclusions 347

References 348

7 Chemotaxonomy seen from a phylogenetic perspective and evolution of secondary metabolism Michael Wink Flavia Botschen Christina Gosmann Holger Schäfer Peter G. Waterman 364

7.1 Introduction 365

7.2 Establishment of chemotaxonomy as a research discipline 365

7.3 Developments in small molecule chemotaxonomy over the past 35 years 380

7.4 Molecular biology and plant taxonomy 382

7.5 Comparison between patterns of secondary metabolites and molecular phylogeny 383

7.6 Evolution of plant secondary metabolism 406

Acknowledgements 426

References 426

Index 434