Total synthesis of LL-Z1271α:
| Reference: | Welch, S. C.; Hagan, C. P.; White, D. H.; Fleming, W.P.; Trotter, J. W. J. Am. Chem. Soc. 1977, 99, 549. DOI |
| Reactions: | Robinson annulation, diketone • Ketone enamine+Enone • Enone+EnAmine • Cyclohexenone • Bicyclo(440) • ConjReduct Enone • ConjReduct-Acylation • Ketone → Alkyl-OH • CompRed-Ketone/Enone+M-H • O-H → O-THP • Ketone enolate+CO2 • CarboxAcid → CarboxEster • ConjReduct-Alkylation • CarboxEster enolate+Alkyl-X • EnoateEster ConjReduct • Alkyl-X+Enolate • Ketone → EnolEther • CarboxEster → CarboxAcid • O-THP → O-H • Ketone → Ketone-α-SeR • Selenide → Selenoxide • Selenoxide-Ei → KetoAldehydeEnone • Aldehyde → Enal • Hydrogenation Enone • Claisen acylation, formate • Ketone enolate+Formate • Mechanism • Jones oxidation • Alkyl-OH → Ketone • Enal → Acetal • Alkene bromination • CarboxAcid → CarboxEster • Lactone-5 • Williamson esterification • Ketone → Ketone-α-Halo • Dehydrohalogenation → Enone • Ketone-α-Halo → Enone • Meyer-Schuster Rearrangement • Lactone-6 • Mechanism • Li-Alkynyl+Ketone • Enone+Li-R • Li/H → Li-Alkynyl • CompE+-Ketone/Lactone+M-R • |
| Reagents: | Methyl vinyl ketone • Hydroxide, potassium • Pyrrolidine • Wieland-Miescher • BH4-Na+ • Li°/NH3 • CO2 • Diazomethane • DHP • NaH • Chloromethyl ether • Li°/NH3 • MeI • Thiolate, propyl • HMPA (solvent) • HMPA (solvent) • CrO3, H2SO4 (Jones) • Br2 • Carbonate, calcium • Br2 • Carbonate, potassium • H2, Rh • Rh(PPh3)3Cl • NaH • Formate, ethyl • SePh-Cl • Perbenzoic acid, 3-chloro • Glycol • DMF (solvent) • Alkynyl-Li • H2SO4 • HOMe (react) • Perbenzoic acid, 3-chloro • |