Potassium Iodide as a Green Electrolyte and Redox Mediator in Electro-Organic Synthesis: Recent Advances and Mechanistic Insights

Potassium iodide (KI), an inexpensive, readily available, and environmentally benign salt, has emerged as an efficient electrolyte and redox mediator in electro-organic synthesis. The dual role of KI enables the in situ generation of reactive iodine species (I●, I+, and I2), facilitating diverse electrochemical transformations under mild and sustainable conditions. This review summarizes recent advances in KI-mediated electrosynthesis, including C–H chalcogenation, halogenation, annulation, cyclization, skeletal rearrangement, oxygenation, and cross-dehydrogenative coupling reactions. Mechanistic studies involving cyclic voltammetry, radical trapping experiments, EPR analysis, isotope labeling, and DFT calculations have highlighted the crucial role of KI in substrate activation, electron-transfer mediation, and catalytic cycle regeneration. The advantages of KI-mediated electrochemistry, such as metal-free conditions, broad substrate scope, operational simplicity, scalability, energy efficiency, and eco-friendliness, are also discussed along with future perspectives in sustainable organic synthesis. In this review, we summarize the recent progress and emerging developments in KI-mediated electrochemical synthesis of organic molecules, focusing on studies reported from 2018 to 2026.