Divergent Synthesis of Thioethers and Thioesters from Arenes and Carboxylic Acids

Synthetic methods that provide divergent access to different product classes from the same starting materials are highly desirable in synthetic chemistry. Here, we report a switchable, catalyst- and thiol-free strategy for the controllable synthesis of thioethers and thioesters from common arenes, carboxylic acids, and tetramethylthiourea. The switchable outcome is governed by the fine-tuning of reaction conditions, which direct the reaction pathway: the in situ-generated thiophenolate anion is diverted toward either a photoinduced decarboxylative route to furnish thioethers or a direct nucleophilic substitution to yield thioesters. The reaction is scalable to gram quantities, proceeds efficiently under natural sunlight, and enables the late-stage modification of complex drug-like scaffolds, underscoring its utility in both synthetic and medicinal chemistry.