Photoredox/Copper Dual-Catalyzed Benzylic C–H Esterification via Radical-Polar Crossover

Herein, we report a distinctive photoredox/copper dual-catalyzed esterification of benzylic C–H bonds through the combination of photoredox-mediated hydrogen atom transfer and Cu­(II)-mediated radical-polar crossover. This methodology demonstrates a high functional group tolerance (>40 examples) and moderate to good yields with structurally diverse benzylic C–H substrates. Notably, stoichiometric amounts of carboxylic acids are used as coupling partners, which allows the synthesis of structurally diverse benzylic esters and the late-stage functionalization of pharmaceuticals.