Total synthesis of Picrotoxinin (Trost):
| Reference: | Trost, B. M.; Krische, M. J. Am. Chem. Soc. 1996, 118, 233 DOI |
| Reactions: | O-H → O-SiMe2tBu • Allyl-OH → Enal • Pinnick oxidation • Enal → EnoateAcid • O-H → O-C(O)R • Ketal → Diol-1,2 • O-SiMe3 → O-H • Enone enolate+Aldehyde • Aldol-Li → Aldol • Nitrile anion+Ketone • Enone+Nitrile anion • Nitrile → Aldehyde • Bromoetherification • Ether-5 • Bicyclo(321)-oxa • Allyl-X → Allyl-OH • Allyl-OR isomerization • Reductive elimination - X/OR • Reductive elimination - OH/OH • Diol-1,2 → Alkene • EnoateEster epoxidation, nucleophilic • Epoxide → Diol • O-SiMe2tBu → O-H • CompE+-Si-O/Si-O+H2O • Pd-Alder-ene • Cyclopentane • Bicyclo(430) • Lactone-5 • Mg-Alkynyl+Aldehyde • Felkin-Anh • O-H → O-SiMe2tBu • Allyl-OH → Allyl-Cl • Epoxidation, peracid • Alkene → Diol-1,2 • Diol-1,2 → Ketal • Lactone-5 • O-H → O-SiMe3 • |
| Reagents: | LiNiPr2 • Formaldehyde • SiMe2tBu-Cl • LiCH2-CN • Tribromide • AlHiBu2 • Bisulfate, sodium • Alkynyl-MgX • SiMe2tBu-Cl • SOCl2 • Carbonate, cesium • Carbonate, potassium • DMSO, (COCl)2 (Swern) • Chlorite, sodium • Diazomethane • Peracetic acid, trifluoro • OsO4 • Zn° • Hydroxide, potassium • Diazomethane • Acetyl chloride • HCl, H2O • SiMe3-OTf • HF • DMF dimethylacetal • Hydroperoxide, tbutyl • LiN(SiMe3)2 • Cyanide, potassium • LiOtBu • Imidazole • Imidazole • Pd(OAc)2 • Fluoride, R4N+ • Lutidine • |