Comprehensive Summary Thioesters and their derivatives serve as prominently featured structural units in biological molecules. However, the lack of an adaptable and efficient synthetic method has hindered their widespread application. In terms of atom‐ and step‐economy, there is an urgent need for an efficient strategy with a wider range of substrates compared to previous methods. Herein, we report a visible‐light‐driven synthesis of structurally diverse thioesters from aryl thianthrenium salts and carboxylic acids, using tetramethylthiourea as both sulfur source and potent photoreductant. This strategy utilizes aryl thianthrenium salts as novel electrophiles, which can be readily prepared via regioselective C–H thianthrenation of arenes. Mechanistic studies reveal that excited‐state thiourea has strong reducing ability and can undergo a facile SET process with aryl thianthrenium salts.
Feng et al. (Thu,) studied this question.