Selective Electroreductive Cross-Coupling of <i>N</i> -Heteroarenes and Aryl Carboxylic Derivatives

The site-specific construction of C(sp³)-C(sp³) bonds via direct reductive cross-coupling between <i>N</i>-heteroarenes and arenes remains an elusive challenge; yet, this underexplored research direction holds significant importance for various fields. Herein, by employing an undivided cell tolerant of air and moisture, we present, for the first time, an electrochemical strategy that enables regioselective C(sp³)-C(sp³) bond formation through the reductive cross-coupling of <i>N</i>-heteroarenes with aryl carboxylic derivatives at room temperature. This transition-metal-free and H₂-free method exhibits broad substrate scope, operational simplicity, and high regio- and chemoselectivity. It offers an efficient platform for diversely accessing α-cycloalkylated cyclic amines─valuable scaffolds with widespread applications across various fields. Mechanistic studies indicate a radical-radical cross-coupling pathway between the α-carbon of <i>N</i>-heteroarenes and the <i>para</i>-position of the carbonyl group in carboxylates. This strategy, merging electroreductive dearomatization with <i>in situ</i> radical transformations, will open new avenues for the development of tandem reactions using abundant, yet less reactive (hetero)arene resources.