Total synthesis of Terpestacin:
| Reference: | Chan, J.; Jamison, T. F. J. Am. Chem. Soc. 2003, 125, 11514. DOI |
| Reactions: | O-H → O-SiMe3 • O-SiiPr3 → O-H • ConjAdd Cu-Alkyl • Cu-Alkyl+Enone • Enone+Cu-R • Alkyne isomerization • Li/I → Li-Alkyl • CompE+-Alkyl-I/Alkynyl-H+M-R • Pauson-Khand • Cyclopentenone • Bicyclo(330)-oxa • Ketone → Ketone-α-OR • Ni-Aldehyde Hydrocarbation • Ketone enolate+Me-I • Ketone enolate+Alkyl-X (intram) • Alkyl-X+Enolate (intram) • CompE+-Si-O/Si-O+H2O • CompE+-Si-O/Si-O+H2O • O-SiMe3 → O-H • CompE+-Si-O/Si-O+H2O • O-SiMe2tBu → O-H • Ketone → Alkyl-OH • Diol-1,2 → Ketone-α-OR • Allyl-OH → Allyl-I • O-H → O-SiiPr3 • |
| Reagents: | NMO • Alkyl-Li • BuLi(tert) • BH4-Na+ • Fluoride, R4N+ • KOtBu • SiMe3-Cl • Fluoride, R4N+ • KN(SiMe3)2 • Carbonate, potassium • CuI • O2 • P(OEt)3 • DMSO (solvent) • Ni(cod)2 • Chiral catalyst (phosphine) • MeI • LiN(SiMe3)2 • SiiPr3-OTf • Hydroxide, sodium • RuO4-Pr4N+, NMO • HCl, H2O • Imidazole • PPh3 • |