Total synthesis of Sieboldine A:
| Reference: | Canham, S. M.; France, D. J.; Overman, L. E. J. Org. Chem. 2013, 78, 9–34. DOI |
| Reactions: | O-SiMe2tBu → O-H • Hydrostannation Alkyne • CarboxEster → Alkyl-OH • Mitsunobu → OR • O-H → O-Alkyl (phenol) • Sn-Vinyl → I-Vinyl • Li/I → Li-Vinyl • Li-R → Ce-R • Ce-Vinyl+Ketone • Ketone+Li-Vinyl • O-H → O-SiEt3 • Alkyl-OSiR3 → Aldehyde • Aldehyde → Alkyne • Seyferth-Gilbert homologation • Cationic cyclization • Cyclopentane • Bicyclo(430) • Semipinacol • Ozonolysis • Dehydroalkoxylation → EnoateEster • Diels-Alder-inverse, EnolEther • Ketone → Alkyl-OH • Epoxidation, dioxirane • Epoxide → Diol • Acetal → Acetal(thio) • Spiro(44)-oxa • N-H → N-Alkyl • N-SO2R → N-H • Acetal → Aminal • Alkyl-OH → Ketone • N-MOM → N-H • Cu-Me+Allyl-X • Allyl-X+Cu-R • Mg-R → Cu-R • Iodolactonization • Lactone → Alkyl-OH • Alkyl-X → Alkyl-H(2°) • O-H → O-SiEt3 • CompNu-O-H/O-H+R3Si-X • Alkyl-OH → Aldehyde • |
| Reagents: | Me-MgBr • CuBr·SMe2 • I2, KI • Bicarbonate, sodium • AlH4-Li+ • Dess-Martin • SiEt3-OTf • Lutidine • SnR3-Li • LiNiPr2 • CuBr·SMe2 • AlHiBu2 • Vinyl-I • I2 • BuLi(sec) • CeCl3 • SiEt3-Cl • Lutidine • DMSO, (COCl)2 (Swern) • Diazophosphonate • Carbonate, potassium • AuCl·L • O3; Me2S • DBU • Vinyl-OR • Eu(fod)3 • AlHiBu2 • Dioxirane • BF3·OEt2 • Fluoride, R4N+ • PPh3, DEAD • Carbonate, potassium • Me2S-SMe+ X- • Pyridine, 2,6-di-tBu • RuO4-Pr4N+, NMO • B(Br)Me2 • PPh3, DIAD • |