Photocatalytic Neophyl Rearrangement and Reduction of Distal Carbon Radicals by Iminyl Radical-Mediated C-C Bond Cleavage

The control of selectivity in the reactions of the highly reactive open-shell carbon radicals is an attractive but often challenging task. Building on the strategy of photoinduced iminyl radical-mediated C-C bond cleavage, we have developed photocatalytic neophyl rearrangement and reduction of distal carbon radicals under visible light irradiation of O-acyl oximes. This mild protocol tolerates a wide range of readily available O-acyl oximes, enabling facile synthesis of diversely substituted alpha,beta-unsaturated nitriles and beta-functionalized saturated nitriles in a highly selective manner.