Electrochemical C(sp 2 )─H Amination of Benzoxazoles Using Liquid DMF as a Safe and Practical Dimethylamino Source

A novel and environmentally benign electrochemical method for the direct C2─H amination of benzoxazoles has been developed. This protocol employs N , N ‐dimethylformamide not only as a solvent but also as the amino source, undergoing anodic decarbonylation to generate a dimethylamino radical. The reaction proceeds under exogenous oxidant‐ and transition metal‐free conditions, utilizing inexpensive iodine as a redox mediator and a catalytic amount of 4‐ tert ‐butylbenzoic acid as an additive. A broad range of substituted benzoxazoles is tolerated, affording the corresponding 2‐(dimethylamino)benzoxazole derivatives in moderate to good yields. The transformation shows excellent functional group compatibility and is scalable to gram‐level. Mechanistic investigations, including radical trapping experiments and cyclic voltammetry, support a radical pathway involving the key formation of a dimethylamino radical intermediate.