Thiol-free arene C–H thioesterification enabled by a photoactive electron donor–acceptor complex

We herein report a catalyst- and thiol-free method for synthesizing thioesters from arenes, carboxylic acids, and tetramethylthiourea in a one-pot process, by combining arene activation <i>via</i> the interrupted Pummerer reaction with an electron donor-acceptor complex strategy. The method enables late-stage modification of complex bioactive molecules, and operates effectively under natural sunlight, highlighting its potential synthetic value.