Photoinduced and Thiophenolate Anion-Enabled Functionalization of Aryl Halides via Catalytic Electron Donor–Acceptor Complex

A visible-light-driven, transition-metal-free functionalization of aryl halides has been developed through a thiophenolate anion-enabled catalytic EDA complex strategy. In contrast to previous EDA-complex-based transformations, where aryl thiolates served as substrates, this approach employs the thiophenolate anion as a catalytic electron donor, facilitating sulfonylation with cost-effective sulfinates as radical acceptors to yield a wide array of aromatic sulfones, including important pharmaceuticals. Furthermore, this strategy supports diverse functionalization, including arylation, borylation, cyanation, and selenylation, enhancing the applicability of aryl halides in environmentally benign photocatalytic systems.