Chemical Synthesis of Hormones, Pheromones and Other Bioregulators

Chemical Synthesis of Hormones, Pheromones and Other Bioregulators......Page 5
Contents......Page 7
Preface......Page 13
Abbreviations......Page 15
1.2 Developmental stages of studies on biofunctional molecules......Page 17
1.3 Small amounts of the samples are now sufficient for the elucidation of the structures of biofunctional molecules......Page 19
1.4 Why must biofunctional molecules be synthesized?......Page 20
1.5.2 What kind of consideration is necessary before starting a synthesis?......Page 21
1.5.5 Criteria for ‘A Good Synthesis’......Page 22
1.6.1 Stereochemistry and reactivity......Page 26
1.6.2 Stereochemistry and analytical methods......Page 27
References......Page 32
2.1.1 What are phytohormones?......Page 35
2.1.2 Gibberellins......Page 36
2.1.3 Diterpenes related to gibberellins......Page 46
2.1.4 Abscisic acid and its relatives—synthesis of optically active compounds......Page 54
2.1.5 Brassinosteroids......Page 57
2.1.6 Phyllanthrinolactone, a leaf-closing factor......Page 61
2.2.2 Synthesis of pisatin......Page 65
2.2.3 Synthesis of 2-(4-hydroxyphenyl)naphthalene-1,8-dicarboxylic anhydride......Page 68
2.2.4 Synthesis of oryzalexins......Page 69
2.2.5 Synthesis of phytocassanes......Page 72
2.3.1 Synthesis of glycinoeclepin A......Page 75
2.3.2 Synthesis of strigolactones......Page 77
2.4.1 Synthesis of arnebinol......Page 83
2.4.2 Synthesis of magnosalicin......Page 84
2.4.3 Synthesis of hernandulcin......Page 85
2.4.4 Synthesis of O-methyl pisiferic acid......Page 87
2.4.6 Synthesis of mispyric acid......Page 89
References......Page 93
3.1.1 What are insect hormones?......Page 97
3.1.2 Synthesis of juvabione......Page 98
3.1.3 Synthesis of the racemates of juvenile hormones......Page 102
3.1.4 Synthesis of the enantiomers of juvenile hormones......Page 104
3.2.1 Synthesis of polygodial......Page 111
3.2.3 Synthesis of 3,4\'-dihydroxypropiophenone 3-β-d-glucopyranoside......Page 113
3.2.4 Synthesis of homogynolide A......Page 115
3.3.1 Synthesis of rotundial......Page 116
3.3.2 Synthesis of polyzonimine......Page 118
References......Page 120
4.2 Methods for enantioselective synthesis......Page 123
4.2.2 Enantiomer separation (optical resolution)......Page 124
4.2.4 Determination of enantiomeric purity......Page 125
4.3 Why is it meaningful to synthesize enantiopure pheromones?......Page 126
4.3.2 Determination of absolute configuration (2). hemiacetal pheromone of Biprorulus bibax......Page 127
4.3.3 Determination of absolute configuration (3). sesquiterpene pheromone of Eysarcoris lewisi......Page 134
4.3.4 Clarification of the relationship between absolute configuration and pheromone activity—exo-brevicomin......Page 138
4.3.5 Clarification of structure (1). lineatin......Page 140
4.3.6 Clarification of structure (2). American cockroach pheromone......Page 142
4.3.7 Clarification of structure (3). acoradiene......Page 145
4.3.8 Clarification of structure (4). himachalene-type pheromone......Page 146
4.3.9 Preparation of a pure sample for bioassay (1). disparlure......Page 149
4.3.10 Preparation of a pure sample for bioassay (2). japonilure......Page 153
4.3.11 Preparation of a pure sample for bioassay (3). pheromone of the palaearctic bee, Andrena wilkella......Page 155
4.4.1 Dihydroactinidiolide, a pheromone component of the red imported fire ant......Page 159
4.4.2 Lardolure, the aggregation pheromone of the acarid mite......Page 161
4.4.3 Pheromone of the fall webworm moth......Page 164
4.4.5 Faranal, the trail pheromone of the pharaoh’s ant......Page 167
4.4.8 (1S,5R)-Frontalin, the bark beetle pheromone......Page 169
4.4.9 (1R,5S,7R)-3,4-Dehydro-exo-brevicomin and (S)-2-sec-butyl-4,5-dihyrothiazole, the pheromone components of the male mouse......Page 172
4.5.1 Sulcatol, the pheromone of Gnathotrichus sulcatus......Page 174
4.5.2 Sex pheromone components of female German cockroach......Page 175
4.5.3 Stigmolone, the pheromone of a myxobacterium Stigmatella aurantiaca......Page 182
4.5.4 Ipsenol and ipsdienol, pheromones of Ips bark beetles......Page 183
4.5.5 Serricornin, the cigarette beetle pheromone......Page 184
4.5.6 Stegobinone, the drugstore beetle pheromone......Page 187
4.5.7 Supellapyrone, the sex pheromone of the brownbanded cockroach......Page 192
4.5.8 Olean, the sex pheromone of the olive fruit fly......Page 194
4.5.9 13,23-Dimethylpentatriacontane as the sex pheromone of a tsetse fly......Page 197
4.6 Significance of chirality in pheromone science......Page 198
References......Page 200
5.1.1 A-factor......Page 205
5.1.2 Sch II and relatives, the fruiting-inducing cerebrosides......Page 207
5.1.3 Basidifferquinone C......Page 211
5.1.4 Sclerosporin......Page 212
5.1.5 Sporogen-AO 1......Page 213
5.1.6 Differolide......Page 215
5.2 Antibiotics......Page 217
5.2.1 Ascochlorin......Page 218
5.2.2 Ascofuranone......Page 220
5.2.3 Trichostatin A......Page 222
5.2.4 Koninginin A......Page 223
5.2.5 Cytoxazone......Page 229
5.2.6 Neuchromenin......Page 230
5.2.7 Nocardione A and B......Page 231
5.2.8 Cytosporone E......Page 232
5.3.2 Pinthunamide......Page 235
References......Page 237
6.1.1 Stypoldione......Page 239
6.1.2 meso- and (±)-Limatulone......Page 242
6.1.3 Testudinariol A......Page 243
6.2.1 Punaglandin 4......Page 248
6.2.2 Bifurcarenone......Page 251
6.2.3 Elenic acid......Page 254
6.2.4 Symbioramide......Page 256
6.2.6 Penaresidin A and B......Page 258
6.2.8 Plakoside A......Page 261
6.3.1 Esterified cerebroside of human and pig epidermis......Page 268
6.3.2 Ceramide B, 6-hydroxylated ceramide in human epidermis......Page 272
6.3.3 KRN7000, a glycosphingolipid that stimulates natural killer T cell......Page 274
6.3.4 Analogs of KRN7000 prepared in 2003–2006......Page 276
6.3.5 Cyclitol, carbasugar and modified d-galactose analogs of KRN7000: RCAI-56 and RCAI-61......Page 278
References......Page 280
7.1 Origin of incorrect or obscure structures......Page 283
7.2.1 Kögl’s auxin-a and -b, the plant-growth promoters......Page 284
7.2.2 Chemical communication system of the green flagellate, Chlamydomonas......Page 286
7.2.3 Early fabrications of the structures of insect pheromones......Page 291
7.3 Incorrect structures resulting from inappropriate use of purification or analytical methods......Page 292
7.4.1 Blattellastanoside A and B, putative components of the aggregation pheromone of the German cockroach......Page 294
7.4.2 2,2,4,4-Tetramethyl-N,N-bis(2,6-dimethylphenyl)cyclobutane-1,3-diimine as a putative antifeedant against the cotton boll weevil......Page 300
7.5 Human errors are inevitable in chemistry, too......Page 301
References......Page 303
8.1 Small molecules are also beautiful......Page 305
8.2 Continuous efforts may bring something meaningful......Page 306
Acknowledgements......Page 307
Index......Page 309