Electrocatalytic oxidation or amidation of olefins by asymmetric electrolytes steering carbocation pathways

Olefin functionalization is a powerful approach for accessing a wide range of value-added compounds with broad applications. Advanced electrosynthesis offers streamlined upgrades over traditional methods by employing electrons as traceless agents and is extremely attractive for promoting olefin functionalization, but achieving high efficiency and selectivity remains a major challenge. Here, we report a conceptually new electrochemical strategy that precisely controls the reactivity of olefin-derived carbocations, the key intermediates of functional transformations, through asymmetric electrolyte design. Using cyclohexene as a model substrate, we reveal that while the local electrode microenvironment steers surface-generated carbocations toward either electrochemical oxidation or Ritter-type amidation in water/acetonitrile mixed electrolytes, the intrinsic competition between water and acetonitrile fundamentally dictates the reaction outcome. By creating a controlled molecular imbalance under overall charge neutrality through selective semipermeable membranes, the asymmetric electrolyte system decouples these competing pathways, enabling exclusive oxidation or 98% selective amidation—the highest Ritter-type amidation efficiency reported under electrochemical conditions. This work establishes electro-driven carbocation control as a powerful principle for resolving intrinsic selectivity challenges in multicomponent systems and provides a broadly applicable, sustainable strategy for selective olefin electro-conversion.