Enantioselective Imino-Ene Reaction of N‑Sulfonyl Ketimines with Silyl Enol Ethers: Access to Chiral Benzosultams

A highly efficient asymmetric imino-ene reaction of cyclic ketimines with silyl enol ethers was developed. Various chiral benzosultam derivatives were obtained in excellent yields (up to 99%), enantioselectivities (up to 99% ee), and diastereoselectivities (up to >19:1 dr) by utilizing a Ni­(BF4)2·6H2O/N,N′-dioxide complex as the catalyst. A possible transition state model was proposed to explain the stereoinduction. Furthermore, the synthetic utility of the protocol provided quick access to optically pure HIV-1 inhibitor.