Photoinduced Copper-Catalyzed Radical Aminocarbonylation of Cycloketone Oxime Esters

A visible light-induced and exogenous photo-sensitizer-free, copper-catalyzed radical aminocarbonylation of cycloketone oxime esters with CO gas and amines is developed. The mild catalytic system involving CuCl and N,N,N-tridentate ligand shows good reactivity and chemo-selectivity, and tolerates a wide range of cycloketone oxime esters and alkyl/aryl amines, giving the corresponding cyanoalkylated amides in moderate to good yields. Preliminary mechanistic studies suggest that the reaction involves a Cu-I/(CuCuIII)-Cu-II/-based catalytic cycle and radical intermediate.