Total synthesis of Gelsemine (Part 2) (Overman):
| Reference: | 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 1) |
| Reactions: | Lactone-6 • Ketone → Ketone-α-OR • EnolSilane → Ketone-α-OH • Ketone → EnolTriflate • Pd-Carboxylation • EnolTriflate → EnoateEster • CarboxEster → Carboxamide • Aziridine • Aziridine+Cyanide • Amine-5 • Lactone → Lactol • CompRed-Lactone/Lactam+M-H • Lactol → Ether • Reductive etherification • Ether-6 • Bicyclo(331)-oxa • Bicyclo(430)-oxa • Pd-Heck coupling • Lactam-5 • Lactone-6 • N-H → N-MOM • Ketone → Alkyl-OH • N-MOM → N-H • Ketone → EnolSilane • EnolEther → Ketone • CompNu-EnolEther/Aminal+H+ • Retro-Aldol • Aldol-Base → Aldol • O-Ethoxyethyl → O-H • Mechanism • N-C(O)R → N-H • O-H → O-Ethoxyethyl • |
| Reagents: | KN(SiMe3)2 • SiEt3-Cl • Iodosobenzene • BF3·OEt2 • KN(SiMe3)2 • Tf2N-2-Py-5-Cl • Tf2N-2-Py-5-Cl • PdCl2(dppf) • CO • NBu3 • AlMe3 • AlMe2-NR2 • Chloromethyl ether • NaH • HCl, H2O • DBU • Vinyl-OR • TsOH·Py • Cyanide, sodium • DMSO (solvent) • MeOTf • Cyanide, sodium • DMSO (solvent) • HCl, H2O • NEtiPr2 • AlHiBu2 • HOMe (react) • HOMe (react) • TsOH·Py • Pyridine, 2,6-di-tBu • Pd2(dba)3 • Ag3PO4 • NEt3 • |