Total synthesis of Gephyrotoxin (Kishi):
| Reference: | Fujimoto, R.; Kishi, Y.; Blount, J. F. J. Am. Chem. Soc. 1980, 102, 7154-7156. DOI |
| Reactions: | Mg-Alkynyl+Imide • CarboxEster → Alkyl-OH • O-H → O-Bn • Alkynyl-OR → EnoateEster • Alkynyl-OR → EnoateEster • CompE+-CarboxEster/CarboxAmide+M-R • EnoateEster Hydrogenation • Ketone → EnAmine • Mg-Alkynyl+Imide • Mg-Alkynyl+Imide • N-H → N-C(O)OR • O-H → O-SO2Me • O-C(O)R → O-H • Alkynyl-OR → EnoateEster • EnAmine alkylation • Amine-6 • Bicyclo(440)-aza • Bicyclo(430)-aza • Hydrogenation Enone • Mg-Alkynyl+Ketone • Ketone+Mg-Alkynyl • Alkyl-OH → Ketone • CompOx-Alkyl-OH/Amine+DMSO • EnoateEster → Allyl-OH • Allyl-OH → Alkyl-OH • Alkyl-OH → Aldehyde • Wittig-alkylidene • Ketone → Allene • Allene synthesis • EnolEther → Enal • O-H → O-SiPh2tBu • Vinyl-Cl → Alkyne • O-SiMe2tBu → O-H • Wittig-chloromethyl • Dehydrohalogenation → Alkyne • O-H → O-C(O)R • |
| Reagents: | Alkynyl-MgX • HCl, H2O • Alkynyl-MgX • HCl, H2O • H2, Pd • O=C(OBn)Cl (Cbz) • BH4-Li+ • KH • Benzyl-X • Hydroxide, barium • TsOH·Py • Sulfonyl chloride, methane, NEt3 • Bromide, lithium • H2, Pt • DMSO, (COCl)2 (Swern) • Acetic anhydride • Alkynyl-MgX • HCl, H2O • Me-MgBr • Imidazole • AlH4-Li+ • CrO3Cl·PyH (PCC) • NaOEt • TsOH • PPh3=C=CHOR • PPh3=CH-Cl • Me-Li • Fluoride, R4N+ • |