Total synthesis of Penitrem D:
| Reference: | Smith, A. B., III; Kanoh, N.; Ishiyams, H.; Hartz, R. A. J. Am. Chem. Soc. 2000, 122, 11254. DOI |
| Reactions: | Ketone azaenolate+Epoxide • Epoxide+Enolate • O-CH2SMe → O-H • O-C(O)R → O-H • Alkyl-X → Alkyl-SeR • Selenide → Selenoxide • Imine → Ketone • Acetal → Lactol • Lactol → Lactone • Lactone-5 • Reductive etherification • Enone → Allyl-OH • CompRed-Enone/Lactone+M-H • Alkyl-OH → Enone • Enone → Allyl-OH • CompRed-Enone/Lactone+M-H • O-H → O-SiEt3 • Alkyl-OH → Ketone • O-H → O-C(O)R • Li/H → Li-Benzyl • Friedel-Crafts Alkylation • Ketone enamine+Aldehyde • Bicyclo(430) • O-H → O-C(O)R • O-SiMe3 → O-H • Aminal • Selenoxide-Ei → Ene • Indole synthesis • Li-Benzyl+Lactone • Lactone+Li-R • Allylic oxidation → Allyl-OH • O-C(O)R → O-H • Mechanism • Ether-6 • Bicyclo(440)-oxa • |
| Reagents: | LiNiPr2 • Benzoyl chloride • BuLi(n) • BuLi(sec) • DMAP • SiMe3-Cl • Acetate, sodium • HClO4 • Cr2O7·2PyH (PDC) • HSiEt3 • Carbonate, potassium • Carbodiimide • Dess-Martin • O2 • BH(sBu3)-Li+ • SiEt3-OTf • DMSO, Py·SO3 (Parikh-Doering) • HCl, H2O • Sc(OTf)3 • Acetic anhydride, DMAP • Fluoride, R4N+ • Selenocyanate, o-nitrophenyl • PBu3 • Perbenzoic acid, 3-chloro • Carbonate, potassium • Benzyl-Li • Epoxide • Lutidine • |