Aqueous pulsed electrochemistry promotes C−N bond formation via a one-pot cascade approach

Abstract Electrocatalytic C − N bond formation from inorganic nitrogen wastes is an emerging sustainable method for synthesizing organic amines but is limited in reaction scope. Integrating heterogeneous and homogeneous catalysis for one-pot reactions to construct C − N bonds is highly desirable. Herein, we report an aqueous pulsed electrochemistry-mediated transformation of nitrite and arylboronic acids to arylamines with high yields. The overall process involves nitrite electroreduction to ammonia over a Cu nanocoral cathode and subsequent coupling of NH 3 with arylboronic acids catalyzed by in situ dissolved Cu(II) under a switched anodic potential. This pulsed protocol also promotes the migration of nucleophilic ArB(OH) 3 − and causes the consumption of OH − near the cathode surface, accelerating C − N formation and suppressing phenol byproducts. Cu(II) can be recycled via facile electroplating. The wide substrate scope, ready synthesis of 15 N-labelled arylamines, and methodological expansion to cycloaddition and Click reactions highlight the great promise.