Total synthesis of Morphine (Taber):
| Reference: | Taber, D. F.; Neubert, T. B.; Rheingold, A. L. J. Am. Chem. Soc. 2002, 124, 12416 DOI |
| Reactions: | Selenide → Selenoxide • O-Me → O-H (phenol) • Mitsunobu → Azide • Alkyl-OH → Alkyl-N3 • Selenoxide-Ei → Allyl-OR • Epoxide → Allyl-OH • Birch reduction • KetoEster dianion+Alkyl-X • Allyl-X+Enolate • Claisen acylation, carbonate • Ketone enolate+Carbonate • Aryl-Br → Aryl-OR • O-H → O-Alkyl (phenol) • Decarboxylation Krapcho • N-H → N-Alkyl • Furst-Plattner diaxial • N-SO2R → N-H • Ozonolysis • N-C(O)OR → N-CH3 • Aldehyde enolate+Alkyl-X • Amine-6 • Alkyl-X+Enolate (intram) • Aldol-K → Enone • Cyclohexenone • Bicyclo(440) • Bicyclo(331)-aza • Mechanism • Carbene insertion • Cyclopentene • Bicyclo(430) • Epoxidation, W • Ketone → Ketal • Ketal → Ketone • Ketone → Alkyl-OH • Azide → Amine • N-H → N-SO2R • Enone → Allyl-OH • O-Me → O-H (phenol) • Ether-5 • N-H → N-C(O)OR • Epoxide+M-SeR • Selenolate+Epoxide • Allyl-OH → Enone • Enone → Allyl-OH • Alkyl-OH inversion • Allyl-OH → Allyl-OR • |
| Reagents: | Carbonate, potassium • Collidine • Na°, ROH • HCl, H2O • O=C(OR)2 • NaOMe • LiNiPr2 • Allyl-Br • Vinyl-Br • Chloride, lithium • Hydrobenzoin • TsOH • Orthoformate • BH(sBu3)-Li+ • Azide, diphenylphosphoryl • AlH4-Li+ • Acetic acid • Sulfonyl chloride, benzene • Ethylene dibromide • O3; PPh3 • BH4-Na+ • B(Br)3 • AlH2(OR)2-Na+ • O=C(OEt)Cl • H2O2, W • Selenolate, phenyl • Periodate, sodium • MnO2 • AlH4-Li+ • B(Br)3 • PPh3, DEAD • DMSO (solvent) • Carbonate, potassium • KN(SiMe3)2 • Chiral auxiliary (ketal) • |