Total synthesis of Sirenin (Corey):
| Reference: | Corey, E.J.; Achiwa, K.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1969, 91, 4318. DOI |
| Reactions: | O-C(O)OR → O-H • O-H → O-THP • O-THP → O-H • Ketone → Alkyl-OH • CompRed-Ketone/CarboxEster+M-H • O-H → O-C(O)R • Dehydroacetoxylation → EnoateEster • Ozonolysis • CompOx-Alkene/Alkene+O3 • HWE → EnoateEster • CompE+-Aldehyde/CarboxEster+M-R • Li-Alkynyl+Alkyl-X • Allyl-X+Li-R • Claisen acylation, carbonate • Ketone enolate+Carbonate • KetoEster → EnoateEster • EnoateEster → Allyl-OH • Diazoketone Cyclopropanation • Cyclohexanone • Bicyclo(410) • CarboxEster → Alkyl-OH • O-H → O-C(O)R • O-THP → O-H • Allyl-OH → Allyl-Br • Alkyne → Alkane • CompRed-Alkyne/Alkene+H2 • Alkyl-OH → Aldehyde • CarboxAcid → CarboxCl • Diazoketone • CarboxCl → Diazoketone • Aldehyde → CarboxAcid • O-C(O)R → O-H • |
| Reagents: | O3 • Zn° • Carbonate, potassium • DHP • AlCl3 • Benzoyl chloride, 2,4,6-trimethyl • Pyridine • TsOH • PBr3 • Alkynyl-Li • TsOH • H2, Ni • CrO3·Py2 (Collins) • Ag2O • Oxalyl chloride • Diazomethane • O=C(OR)2 • NaH • BH4-Na+ • Benzoyl chloride • KOtBu • AlCl3 • CuSO4 • |