Total synthesis of Silphinene:
| Reference: | Crimmins, M. T.; Mascarella, S. W. J. Am. Chem. Soc. 1986, 108, 3435 DOI |
| Reactions: | EnolEther → Ketone • Saegusa oxidation • Ketone → Enone • ConjAdd-Alkylation • Enone+Cu-R • Cu-Alkyl+Enone • ConjAdd Cu-Alkyl • Ketone enolate+Alkyl-X • Bromoacetate+Enolate • Mg-R → Cu-R • Aldol-Na → KetoEsterEnone • Cyclopentenone • Bicyclo(330) • Cu-Me+Enone • Ketone → EnolSilane • Alkyl-X → Alkyl-H • Radical reduction(C-I) • Cyclobutane opening • EnolPhosphate → Vinyl-H • Decarboxylation Krapcho • Photochemistry 2+2 • DeMayo cycloaddition • Cyclobutane • Bicyclo(320) • Bicyclo(330) • Ketone → Enolphosphate • |
| Reagents: | Alkyl-MgX • CuI·PBu3 • Allyl-I • HClO4 • NaOMe • Me-Cuprate • Chloride, lithium • Fluoride, R4N+ • Pd(OAc)2 • Quinone • SiMe3-I • Acetonitrile (solvent) • HSnBu3 • LiNiPr2 • P(O)(OR)2Cl • NHMe2 • Photochemistry • |