Photoredox Nickel- or Copper-Catalyzed C-Heteroatom Cross-Coupling of Thianthrenium Salts.

C-heteroatom bonds represent core structural motifs within the scaffolds of pharmaceuticals, agrochemicals, and functional materials. Consequently, developing mild and efficient methodologies for their construction is of paramount importance in modern organic synthesis. Herein, we present a visible-light-driven metallaphotoredox platform that leverages either nickel or copper co-catalysis for the efficient cross-coupling of ArTT salts with diverse heteroatom nucleophiles. This synergistic strategy facilitates the rapid construction of C-S, C-N, and C-O bonds under exceptionally mild conditions. The protocol exhibits a remarkably broad substrate scope and excellent functional group tolerance, proving to be highly compatible with a wide array of thiol and amine nucleophiles. Furthermore, for phenolic substrates exhibiting poor reactivity under our nickel-catalyzed system, the desired C-O bond formation was successfully achieved by pivoting to a photoredox/copper dual-catalytic regime. Furthermore, this method is readily amenable to continuous-flow scale-up without compromising catalytic efficiency, thereby underscoring its robust practical utility.