Polysulfide Anions as Visible Light Photoredox Catalysts for Aryl Cross-Couplings

Polysulfide anions are endowed with unique redox properties, attracting considerable attentions for their applications in alkali metals–sulfur batteries. However, the employment of these anionic species in redox catalysis for small molecule synthesis remains underdeveloped due to their moderate–poor electrochemical potential in the ground state, whereas some of them are characterized by photoabsorptions in visible spectral regions. Herein, we disclose the use of polysulfide anions as visible light photoredox catalysts for aryl cross-coupling reactions. The reaction design enables single-electron reduction of aryl halides upon the photoexcitation of tetrasulfide dianions (S₄^2–). The resulting aryl radicals are engaged in (hetero)­biaryl cross-coupling, borylation, and hydrogenation in a redox catalytic regime involving S₄^• –/S₄^2– and S₃^• –/S₃^2– redox couples.