Total synthesis of Bilobalide (Crimmins):
| Reference: | Crimmins, M. T.; Jung, D. K.; Gray, J. L. J. Am. Chem. Soc. 1993, 115, 3146-3155 DOI |
| Reactions: | Li-R → Ce-R • Alkyl-OH → Ketone • O-SiMe2tBu → O-H • Li-Alkyl+Aldehyde • Nitrile anion+Aldehyde • Nitrile → Aldehyde • Aldol-Li → Aldol • Enone enolate+Aldehyde • Ketone → Ketone-α-OR • Ketone-α-OH cleavage • Aldehyde → Acetal(Me) • Baeyer-Villiger • Lactone-5 • Lactol → Lactone • Lactone-5 • Epoxidation, dioxirane • Diol-1,2 cleavage • Photochemistry 2+2 • Cyclobutane • Cyclopentane • Bicyclo(320) • Bicyclo(320)-oxa • CarboxEster → Alkyl-OH • Lactol → Lactone • Lactone-5 • O-H → O-C(O)R (enol) • O-H → O-SiMe3 • |
| Reagents: | BuLi(tert) • CeCl3 • DMSO, (COCl)2 (Swern) • LiCH2-CN • AlHiBu2 • Butadiene, 2-OR • Fluoride, potassium • Piv-Cl • SiMe3-Cl • MoOPH • Pb(OAc)4 • HOMe (react) • TsOH • HOMe (react) • AlH4-Li+ • Pb(OAc)4 • CrO3, H2SO4 (Jones) • Dioxirane • CrO3, H2SO4 (Jones) • Perbenzoic acid, 3-chloro • |