Total synthesis of Gephyrotoxin (Smith):
| Reference: | Chu, S.; Wallace, S.; Smith, M. D. Agew. Chem. Int. Ed. 2014, 53, 13826 –13829. DOI |
| Reactions: | N-Boc → N-H • O-SiMe2tBu → O-H • Wittig-methoxymethyl • Mg-Alkyl+CarboxAmide • CarboxAmide+Mg-R • Ozonolysis • Wittig-ketomethyl → Enone • CompE+-Aldehyde/Ketone+Wittig • ConjAdd EnAmine • Enone+EnAmine • Ketone → EnAmine • Amine-6 • Cyclohexane • Bicyclo(440)-aza • Bicyclo(430)-aza • EnolPhosphate → Alkyne • Ketone → Alkyne • Ketone → EnolPhosphate • Alkyne → In-Vinyl • Pd/In-Vinyl+Alkynyl-I • Si-Alkynyl → H-Alkynyl • Iminium → Amine • O-H → O-SiMe2tBu • N-H → N-Boc • Alkyl-OH → Aldehyde • CompOx-Alkyl-OH/Amine+DMSO • Imine → Amine • EnolEther → Aldehyde • Aldehyde → Alkyl-OH • |
| Reagents: | Alkyl-MgX • PPh3=CH-COMe • KN(SiMe3)2 • Alkynyl-I • Alkynyl-SiR3 • SiMe2tBu-Cl • Boc2O • BF3·OEt2 • BH(sBu3)-Li+ • KN(SiMe3)2 • O3 • PPh3 • Acetic acid, trifluoro • BH(OAc)3-Na+ • NEt3 • LiTMP • P(O)(OR)2Cl • LiTMP • HCl, H2O • BH4-Na+ • InHCl2 • BEt3 • Acetic acid • Pd2(dba)3 • Carbonate, potassium • DMSO, (COCl)2 (Swern) • PPh3=CH-OR • DMAP • |