Total synthesis of Alnusenone:
| Reference: | Ireland, R. E.; Dawson, M. I.; Welch, S. C.; Hagenbach, A.; Bordner, J.; Trus, B. J. Am. Chem. Soc., 1973, 95, 7829–7841. DOI |
| Reactions: | Robinson annulation, ketone • Ketone enolate+Enone • Cyclohexenone • Bicyclo(440) • ConjAdd M-CN • Nitrile → Aldehyde • Aldehyde → CH3 • Friedel-Crafts Alkylation • Bicyclo(440) • O-Me → O-H (phenol) • Birch alkylation • Enone enolate+Alkyl-X • Alkyl-X+Enolate • Enone → Allyl-OH • Simmons-Smith • Cyclopropane • Bicyclo(410) • Alkyl-OH → Ketone • Ketone enolate+Me-I • O-H → O-Me (phenol) • Cyclopropane Hydrogenolysis • Ketone → Alkyl-OH • O-H → O-P(O)X2 • Alkyl-OH → Alkyl-H • Birch reduction • Enone enolate+Alkyl-X • Deconjugative alkylation • Alkyl-X+Enolate • Mg-Alkyl+Ketone • CompE+-Ketone/Nitrile+M-R • Dehydration → Ene • |
| Reagents: | Hydroxide, potassium • AlEt3 • HCN • Me-MgI • SOCl2 • AlHiBu2 • Hydrazine • TsOH • Li°/NH3 • MeI • AlH(OtBu)3-Li+ • CH2I2, Zn/Cu • CrO3·Py2 (Collins) • KOtBu • MeI • Li°/NH3 • AlH4-Li+ • BuLi(n) • Li°/NH3 • KOtBu • MeI • Cyanide, AlR2 • |