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1 About this book, and how to use it 1 The subject 1 The aim 1 The approach 2 The topics 2 The figures 2 Further reading 3 What to study 3 What to learn 3 Nomenclature 3 Conventions regarding acids, bases, and ions 4 Some common abbreviations 4 Further reading 5 2 Secondary metabolism: the building blocks and construction mechanisms 7 Primary and secondary metabolism 7 The building blocks 8 The construction mechanisms 11 Alkylation reactions: nucleophilic substitution 12 Alkylation reactions: electrophilic addition 12 Wagner-Meerwein rearrangements 15 Aldol and Claisen reactions 15 Imine formation and the Mannich reaction 18 Amino acids and transamination 20 Decarboxylation reactions 22 Oxidation and reduction reactions 24 Dehydrogenases 24 Oxidases 26 Monooxygenases 26 Dioxygenases 26 Amine oxidases 27 Baeyer-Villiger monooxygenases 27 Phenolic oxidative coupling 28 Halogenation reactions 28 Glycosylation reactions 31 Elucidating biosynthetic pathways 34 Further reading 38 3 The acetate pathway: fatty acids and polyketides 39 Fatty acid synthase: saturated fatty acids 39 Unsaturated fatty acids 44 Uncommon fatty acids 53 Prostaglandins 58 Thromboxanes 64 Leukotrienes 64 Polyketide synthases: generalities 66 Polyketide synthases: macrolides 68 Polyketide synthases: linear polyketides and polyethers 90 Diels-Alder cyclizations 96 Polyketide synthases: aromatics 96 Cyclizations 99 Post-polyketide synthase modifications 103 Starter groups 116 Further reading 131 4 The shikimate pathway: aromatic amino acids and phenylpropanoids 137 Aromatic amino acids and simple benzoic acids 137 Phenylpropanoids 148 Cinnamic acids and esters 148 Lignans and lignin 152 Phenylpropenes 156 Benzoic acids from C6C3 compounds 157 Coumarins 161 Aromatic polyketides 166 Styrylpyrones, diarylheptanoids 166 Flavonoids and stilbenes 167 Flavonolignans 173 Isoflavonoids 174 Terpenoid quinones 178 Further reading 184 5 The mevalonate and methylerythritol phosphate pathways: terpenoids and steroids 187 Mevalonic acid and methylerythritol phosphate 188 Hemiterpenes (C5) 192 Monoterpenes (C10) 193 Irregular monoterpenes 204 Iridoids (C10) 206 Sesquiterpenes (C15) 210 Diterpenes (C20) 223 Sesterterpenes (C25) 234 Triterpenes (C30) 234 Triterpenoid saponins 242 Steroids 247 Stereochemistry and nomenclature 247 Cholesterol 248 Phytosterols 251 Vitamin D 256 Steroidal saponins 259 Cardioactive glycosides 265 Bile acids 275 Adrenocortical hormones/corticosteroids 277 Semi-synthesis of corticosteroids 277 Progestogens 287 Oestrogens 290 Androgens 296 Tetraterpenes (C40) 298 Higher terpenoids 306 Further reading 306 6 Alkaloids 311 Alkaloids derived from ornithine 311 Polyamines 311 Pyrrolidine and tropane alkaloids 312 Pyrrolizidine alkaloids 324 Alkaloids derived from lysine 326 Piperidine alkaloids 326 Quinolizidine alkaloids 328 Indolizidine alkaloids 330 Alkaloids derived from nicotinic acid 331 Pyridine alkaloids 331 Alkaloids derived from tyrosine 336 Phenylethylamines and simple tetrahydroisoquinoline alkaloids 336 Modified benzyltetrahydroisoquinoline alkaloids 346 Phenethylisoquinoline alkaloids 359 Terpenoid tetrahydroisoquinoline alkaloids 363 Amaryllidaceae alkaloids 365 Alkaloids derived from tryptophan 366 Simple indole alkaloids 366 Simple β-carboline alkaloids 369 Terpenoid indole alkaloids 369 Quinoline alkaloids 380 Pyrroloindole alkaloids 385 Ergot alkaloids 387 Alkaloids derived from anthranilic acid 395 Quinazoline alkaloids 395 Quinoline and acridine alkaloids 396 Alkaloids derived from histidine 398 Imidazole alkaloids 398 Alkaloids derived by amination reactions 400 Acetate-derived alkaloids 401 Phenylalanine-derived alkaloids 401 Terpenoid alkaloids 406 Steroidal alkaloids 406 Purine alkaloids 413 Caffeine 413 Saxitoxin and tetrodotoxin 416 Further reading 417 7 Peptides, proteins, and other amino acid derivatives 421 Peptides and proteins 421 Ribosomal peptide biosynthesis 422 Peptide hormones 426 Thyroid hormones 426 Hypothalamic hormones 427 Anterior pituitary hormones 429 Posterior pituitary hormones 430 Pancreatic hormones 432 Interferons 433 Opioid peptides 434 Ribosomal peptide toxins 434 Enzymes 438 Non-ribosomal peptide biosynthesis 438 Modified peptides: penicillins, cephalosporins, and other β-lactams 458 Penicillins 458 Cephalosporins 465 Other β-lactams 469 Cyanogenic glycosides 476 Glucosinolates 477 Cysteine sulfoxides 480 Further reading 481 8 Carbohydrates 485 Monosaccharides 485 Oligosaccharides 490 Polysaccharides 493 Aminosugars and aminoglycosides 498 Further reading 507 Index 509