Photo-induced carboxylation of C(sp2)−S bonds in aryl thiols and derivatives with CO2

Abstract Aryl thiols have proven to be a useful class of electron donors and hydrogen atom sources in photochemical processes. However, the direct activation and functionalization of C(sp2)–S bonds in aryl thiols remains elusive in the field of photochemistry. Herein, a photochemical carboxylation of C(sp2)–S bonds in aryl thiols with CO2 is reported, providing a synthetic route to important aryl carboxylic acids. Moreover, different kinds of aryl thiol derivatives, benzeneselenol and diphenyl diselenide also show moderate-to-high reactivity in this transformation. Mechanistic studies, including DFT calculations, suggest that the in situ generated carbon dioxide radical anion (CO2 •−) and disulfide might be the key intermediates, which undergo radical substitution to yield products. This reaction features mild and catalyst-free conditions, good functional group tolerance and wide substrate scope. Furthermore, the efficient degradation of polyphenylene sulfide highlights the usefulness of this methodology.