Total synthesis of Longifolene (Johnson):
| Reference: | Volkmann, R. A.; Andrews, G. C.; Johnson, W. S. J. Am. Chem. Soc. 1975, 97, 4777–4779. DOI |
| Reactions: | ConjAdd Cu-Alkyl • Cu-Alkyl+Enone • Enone+Cu-R • ConjAdd-Acylation • EnolAcetate → Enolate • Dehydrohalogenation → Enone • Ketone-α-Halo → Enone • Enone → Allyl-OH • Cationic cyclization • Cycloheptane • Bicyclo(221) • Alkyl-OH → Alkyl-H(3°) • Alkene isomerization • Alkene cleavage • Ketone enolate+Me-I • Ketone+Li-Alkyl • Li-Me+Ketone • Dehydration → Ene • Ketone → C=CH2 • Mechanism • Ketone enolate+Br2 • |
| Reagents: | Acetyl chloride • Br2 • AlH4-Li+ • ZnBr2 • Acetic acid, trifluoro • BH3CN-Na+ • TsOH • Periodate, sodium • RuO4 • LiNiPr2 • MeI • SOCl2 • |