Total synthesis of Hirsutene (Ley):
| Reference: | Ley, S. V.; Murray, P.J. Chem. Commun. 1982, 1252. DOI |
| Reactions: | Ketone → Ketone-α-SeR • CarboxEster → Alkyl-OH • Selenoxide-Ei → KetoEsterEnone • KetoEster → Enone • CarboxEster → CarboxEster-α-SeR • Alkyl-X → Alkyl-SeR • Cu-Alkyl+Enone • Enone+Cu-R • ConjAdd Cu-Alkyl • Mg-R → Cu-R • Hydrogenolysis C-Se • Alkyl-SeR → Alkyl-H • Ketone protection enolate • Hydrogenolysis C-Se • Alkyl-SeR → Alkyl-H • Mechanism • Cationic cyclization • Cyclopentane • Bicyclo(330) • Wittig-methyl • |
| Reagents: | Alkyl-MgX • NaH • SePh-Cl • H2O2 • RaNi • LiNiPr2 • AlH4-Li+ • Imidazole • PBu3 • RaNi • PPh3=CH2 • CuBr·SMe2 • DMSO (solvent) • Imidazole • SnCl4 • |