Electrochemically Driven Direct Participation of Chalcogenophenols in 1,2-Thio/Seleno-Heteroarylation of Alkenes.

Herein, we report an electrochemically driven three-component strategy that successfully achieves direct coupling of nonpreactivated chalcogenophenols with styrenes and N-heteroarenes, enabling efficient construction of the biologically significant β-azaaryl chalcogenoether. The key to this strategy lies in an anodic oxidation-mediated deprotonation-oxidation pathway, which cleverly circumvents the thermodynamic barrier posed by the bond dissociation energy (∼360 kJ/mol) of the S/Se-H bond in chalcogenophenols. This process generates key thiyl radical intermediates from the thiolate anion in situ, which subsequently undergo a radical-polar crossover to accomplish difunctionalization. The reaction operates without metal catalysts or stoichiometric oxidants, exhibits high atom economy (with hydrogen gas as the sole byproduct), and demonstrates excellent functional group compatibility and a broad substrate scope. Mechanistic studies reveal that the cathodic hydrogen evolution reaction effectively drives the reaction equilibrium. This work provides a concise and reversible approach for C-S/Se bond formation and establishes a new paradigm for electrochemical activation of S-H/Se-H bonds.