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. Synergistic benefits: Visible‐light irradiation is combined with an electrochemical reaction that uses iodine as a redox mediator to enable efficient intramolecular C−H amination. The combined photo/electrochemical approach allows the reactions to proceed with low anode potentials, and thus results in tolerance of a wide range of functional groups.