Total synthesis of Maoecrystal Z:
| Reference: | Cha, J. Y.; Yeoman, J, T. S.; Reisman, S. E. J. Am. Chem. Soc. 2011, 133, 14964–14967.. DOI |
| Reactions: | Selenide → Selenoxide • O-SiMe2tBu → O-H • CarboxAmide enolate(Myers)+Alkyl-X • Alkyl-X+Enolate (asym) • CarboxAcid → CarboxAmide • CarboxAmide → Alkyl-OH • Lactone enolate+Alkyl-X • Alkyl-X+Enolate • Lactone → EneLactone • Selenoxide-Ei → EneLactone • Radical cyclization(Ketyl) • Cyclohexane • Cyclopentane • Bicyclo(430) • Aldehyde → Enal • O-H → O-SiMe2tBu • Epoxide reductive alkylation • Lactone-5 • Spiro(55)-oxa • Epoxidation, peracid • Alkyl-OH → Aldehyde • O-C(O)R → O-H • CompE+-CarboxEster/Lactone+H2O • Ozonolysis • Mannich • Alkyl-OH → Alkyl-I • O-H → O-C(O)R • |
| Reagents: | Chiral auxiliary (amide-Myers) • Piv-Cl • Pseudoephedrine • LiNiPr2 • BH3·NH3 • LiNiPr2 • PPh3, I2 • LiN(SiMe3)2 • KN(SiMe3)2 • SePh-Br • H2O2 • H2SiF6 • SmI2 • Acetic anhydride • O3 • CH2=NMe2+I- • Hydroxide, sodium • Dess-Martin • Imidazole • Acrylate • Perbenzoic acid, 3-chloro • HMPA (solvent) • |