Regiodivergent Electrochemical C–H Aminomethylation of Azaarenes

Abstract

Regioselective C–H functionalization reactions offer a direct and efficient approach to rapidly increase molecular complexity. While several methods enable access to specific regioisomers, achieving regiodivergent C–H functionalization of azaarenes remains a significant challenge. In this work, we present a regiodivergent electrochemical C–H functionalization strategy that allows selective aminomethylation at the C4 or C3 positions of azaarenes by simply varying the solution conditions. The reactions proceed through paired electrolysis, where the anode and cathode cooperate to achieve the desired C–H aminomethylation. Notably, this method utilizes stable, easily handled amides as the aminomethylation agents, eliminating the need for highly electrophilic reagents. These proof-of-concept examples open up exciting opportunities for the regiodivergent C–H functionalization of azaarenes.