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

Direct amination of C(sp³ )-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(sp³ )-H/N-H coupling that exhibits good reactivity with both sp² and sp³ 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.