Modular reductive radical-polar crossover-based acyl migration reactions of <i>N</i>-vinylimides with alkyl, silyl, and acyl radicals

Herein, novel SET reduction-based N → C acyl migration protocols for the preparation of functionalized α-amino ketones were successfully developed. In addition to alkyl and silyl radicals, acyl radicals derived from dihydroquinazolinones or acyl oxime acetates could react with enamides to give various 1,4-diketones. These photocatalytic radical addition/acyl migration cascade reactions feature broad substrate scope, good functional group compatibility, and mild reaction conditions.