Catalytic Asymmetric Polycyclization of Tertiary Enamides with Silyl Enol Ethers: Total Synthesis of (-)-Cephalocyclidin A.
Qing-Bo ZhuangJin-Rui TianKa LuXiao-Ming ZhangFu-Min ZhangYong-Qiang TuRong FanZhi-Hao LiYu-Dong ZhangPublished in: Journal of the American Chemical Society (2023)
A catalytic enantioselective polycyclization of tertiary enamides with terminal silyl enol ethers has been developed by virtue of Cu(OTf) 2 catalysis with a novel spiropyrroline-derived oxazole (SPDO) ligand. This tandem reaction offers an effective approach to assemble bicyclic and tricyclic N -heterocycles bearing both aza - and oxa -quaternary stereogenic centers, which are primal subunits in a range of natural alkaloids. Strategic application of this methodology and a late-stage radical cyclization as key steps have been showcased in the concise total synthesis of (-)-cephalocyclidin A.