Total synthesis of Gelsemine (Hart):
| Reference: | Ataraschi, S.; Choi, J-K.; Ha, D-C.; Hart, D.J.; Kuzmich, D.; Lee, C-S.; Ramesh, S.; Wu, S. C. J. Am. Chem. Soc., 1997, 119, 6226-6241 DOI |
| Reactions: | Diels-Alder, Maleic anhydride • Mg-Aryl+Carboxester • CarboxEster+Mg-R • O-H → O-Me • Ketal → Ketone • N-H → N-C(O)R • Ketone → EnolCarboxylate • Wittig-ketomethyl → Enone • Ketone → EnolSilane • Selenoxide-Ei → Ene • Alkyl-OH → Alkyl-SeR • CarboxImide → Imine • CarboxAmide enolate+Alkyl-X • Alkyl-X+Enolate • Wittig-carboxymethyl → EnoateEster • Ketone enolate+Isocyanate • Radical cyclization(Aryl) • Lactam-5 • Reductive etherification • Ether-6 • Petasis reagent • Aldehyde → C=CH2 • Radical cyclization(Alkyl) • Cyclopentane • Bicyclo(321) • Ketone → Ketal • O-THP → O-H • Ozonolysis • Alkyl-OH → Aldehyde • O-Bn → O-H • Ozonolysis • Dehydroalkoxylation → Ene • O-C(O)R → O-H • Aldehyde epimerization • O-H → O-Alkyl • |
| Reagents: | PPh3 • LiNiPr2 • SiMe3-Cl • Butadiene, 2-OR • Maleic anhydride • TsOH • Glycol • Selenocyanate, o-nitrophenyl • PBu3 • H2O2 • BH4-Na+ • NaH • LiNiPr2 • Chloromethyl ether • O3 • Formate, ethyl • Thiol, phenyl • TsOH • Aryl-MgX • MeI • DMSO (solvent) • KH • Isocyanate • TsOH • Acetic anhydride, DMAP • HSnBu3 • TsOH • O3 • HCl, H2O • HSiEt3 • Acetic acid, trifluoro • AIBN • B(Br)3 • Dess-Martin • TiCp2Me2 (Petasis) • HSnBu3 • AIBN • |