Electrochemical Steady-State Regulation of Pd 0 Enables a Switchable Suzuki–Miyaura Coupling Reaction

Catalyst deactivation via Pd0 oxidation limits Suzuki–Miyaura coupling under aerobic conditions. An electrochemical buffering strategy continuously regenerates Pd0 in a membrane-divided cell, driving PdII/Pd0 equilibrium toward active catalyst. Optimal conditions (40 °C, 0.5 M K2CO3, −0.5 V vs RHE) achieve 99.5% yield with 90% Faradaic efficiency. Spatial separation of cathodic reduction and anodic oxidation confines oxidative species, enabling robust turnover under ambient atmosphere. This electrically regulated platform transforms biaryl synthesis into a scalable, tunable process.