Direct Photocatalytic Synthesis of Medium‐Sized Lactams by C−C Bond Cleavage

Reported is a novel two-step ring-expansion strategy for expeditious synthesis of all ring sizes of synthetically challenging (hetero)aryl-fused medium-sized lactams from readily available 5-8-membered cyclic ketones. This step-economic approach features a remote radical (hetero)aryl migration from C to N under visible-light conditions. Broad substrate scope, good functional-group tolerance, high efficiency, and mild reaction conditions make this procedure very attractive. In addition, this method also provides expedient access to 13-15-membered macrolactams upon an additional one-step manipulation. Mechanistic studies indicate that the reaction involves an amidyl radical and is promoted by acid.