Total synthesis of Sirenin (Grieco):
| Reference: | Grieco, P. A. J. Am. Chem. Soc. 1969, 91,5660. DOI |
| Reactions: | HWE → EnoateEster • Diazoketone Cyclopropanation • Cyclohexanone • Bicyclo(410) • Mg-Allyl+Allyl-X • Hydroboration → Alkyl-OH • CompRed-Alkene/Alkene+M-H • Alkyl-OH → CarboxAcid • Diazoketone • CarboxCl → Diazoketone • Ozonolysis • Claisen acylation, formate • Ketone enolate+Formate • Enol → EnolEther • EnolEther → Enal • EnoateEster → Allyl-OH • CarboxAcid → CarboxCl • Enone → Allyl-OH • CompRed-Ketone/CarboxEster+M-H • |
| Reagents: | Allyl-MgX • NaH • BH(Siam)2 • H2O2, NaOH • CrO3, H2SO4 (Jones) • SOCl2 • Diazomethane • O3; Me2S • HMPA (solvent) • HI • NaH • BH4-Na+ • HCl, H2O • AlH4-Li+ • HMPA (solvent) • |