Total synthesis of Gelsemine (Part 1) (Overman):
| Reference: | Earley, W. G.; Jacobsen, J. E.; Madin, A.; Meier, J. P.; O'Donnell, C. J.; Oh, T.; Old, D. W.; Overman, L. E.; Sharp, M. J. J. Am. Chem. Soc. 2005, 1127, 18046. DOI (Part 2) |
| Reactions: | Diels-Alder, EnoateEster • Bicyclo(222) • Birch reduction • O-SiEt3 → O-H • Ketone → EnolSilane • Wittig-methyl → Diene • CompE+-Aldehyde/CarboxEster+Wittig • Aza-Claisen • Amine-6 • Bicyclo(440)-aza • EnAmine → EnAmine-β-Br • CompNu-Enamide/Alkene+Br2 • Mannich • Amine-5 • Bicyclo(321) • Mechanism • Curtius • C-CO2H → C-N • Allylic oxidation → Enal • CyanoAmine • N-H → N-Alkyl • Cyanide+Aldehyde • EnolCarbonate → Ketone • CompE+-Carbonate/Carbamate+H2O • CarboxEster → CarboxAcid • CompE+-CarboxEster/O-Si+H2O • N-C(O)OR → N-H • N-H → N-C(O)OR • CarboxAcid → CarboxAzide • |
| Reagents: | Butadiene, 1-OR • LiNiPr2 • SiiPr3-OTf • Acrylate • AlCl3 • SeO2 • PPh3=CH2 • Hydroxide, potassium • Azide, diphenylphosphoryl • Acetic acid, trifluoro • Formaldehyde • Fluoride, R4N+ • KH • 18-crown-6 • O=C(OMe)Cl • Hydroxide, potassium • Br2 • Piperidine, pentamethyl • Acetic acid, trifluoro • |