Merging Photochemistry with Electrochemistry: Functional‐Group Tolerant Electrochemical Amination of C(sp3)−H Bonds

Abstract Direct amination of C(sp 3 )−H bonds is of broad interest in the realm of C−H functionalization because of the prevalence of nitrogen heterocycles and amines in pharmaceuticals and natural products. Reported here is a combined electrochemical/photochemical method for dehydrogenative C(sp 3 )−H/N−H coupling that exhibits good reactivity with both sp 2 and sp 3 N−H bonds. The results show how use of iodide as an electrochemical mediator, in combination with light‐induced cleavage of intermediate N−I bonds, enables the electrochemical process to proceed at low electrode potentials. This approach significantly improves the functional‐group compatibility of electrochemical C−H amination, for example, tolerating electron‐rich aromatic groups that undergo deleterious side reactions in the presence of high electrode potentials.