Site‐Selective Electrochemical C−H Carboxylation of Arenes with CO2

Herein, a direct, metal‐free, and site‐selective electrochemical C−H carboxylation of arenes by reductive activation using CO2 as the economic and abundant carboxylic source was reported. The electrocarboxylation was carried out in an operationally simple manner with high chemo‐ and regioselectivity, setting the stage for the challenging site‐selective C−H carboxylation of unactivated (hetero)arenes. The robust nature of the electrochemical strategy was reflected by a broad scope of substrates with excellent atom economy and unique selectivity. Notably, the direct and selective C−H carboxylation of various challenging arenes worked well in this approach, including electron‐deficient naphthalenes, pyridines, simple phenyl derivatives, and substituted quinolines. The method benefits from being externally catalyst‐free, metal‐free and base‐free, which makes it extremely attractive for potential applications. A general and selective approach for the electrochemical C−H carboxylation of arenes with CO2 has been developed to obtain the valuable aromatic carboxylic acids with excellent atom economy. High levels of chemo‐ and regioselectivity were achieved by this electrochemical reductive activation strategy.