Total synthesis of Mesembrine (Keck):
| Reference: | Keck, G. E.; Webb, R. R. J. Org. Chem. 1982, 47, 1302. DOI |
| Reactions: | O-H → O-C(O)R • CarboxAcid → CarboxCl • CarboxAcid → CarboxHydroxamate • Ketone → Ketal • Claisen-Ireland • Diels-Alder, Nitroso • Nitroso Cycloaddition • Li-Aryl+Ketone • Enone-β-OR+Li-R • Enone-β-OR → Enone • Stork-Danheiser • Nitroso ene • Lactam-5 • Retro-Diels-Alder → Nitroso • Bicyclo(430)-aza • Mechanism • N-OR → N-H • Radical reduction(C-Br) • Alkyl-X → Alkyl-H(2°) • N-H → N-Me • Alkene → Bromohydrin • Alkyl-OH → Ketone • N-C(O)R → N-CH2R • Amine-5 • Enone → Allyl-OH • N-OH → N=O • CarboxEster → Ketene acetal • |
| Reagents: | LiNiPrCy • SiMe2tBu-Cl • Aryl-Li • BH4-Na+ • Acetic anhydride, Py • SOCl2 • NH2OH • Periodate, R4N+ • TiCl3 • MeI • NBS • HSnBu3 • CrO3Cl·PyH (PCC) • Glycol • AlH4-Li+ • Carbonate, sodium • AIBN • |