Total synthesis of Crinine (Whitlock) New:
| Reference: | Whitlock, H. W.; Smith, G. L. J. Am. Chem. Soc., 1967, 89, 3600 DOI |
| Reactions: | Pictet-Spengler • Amine-6 • Bicyclo(321)-aza • Nitrile anion+CarboxEster • CarboxEster+Nitrile anion • Nitrile → CarboxEster • Decarboxylation β-keto acid • Claisen acylation, ester • Ketone enolate+CarboxEster • Cyclohexanone • Aziridine • ConjAdd Amine • ConjAdd-Elimination • Imine → Amine • Ketone → Ketone-α-Halo • Dehydrohalogenation → Enone • Ketone-α-Halo → Enone • Allyl-OR isomerization • 1,3-Sigmatropic • Amine-5 • Bicyclo(430)-aza • Enone → Allyl-OH • O-H → O-SO2Ar • CarboxEster → CarboxAcid • Enol → Vinyl-Cl • |
| Reagents: | NaOEt • HCl, EtOH • HCl, AcOH • NaOMe • H2SO4 • Aziridine • H2, Pt • Formaldehyde • Br2 • HOEt (react)} • Iodide, sodium • NEt3 • HCl, H2O • Chloride, lithium • DMF (solvent) • AlH4-Li+ • BuLi(n) • Bicarbonate, sodium • TsCl • |