Electron-transfer-mediated generation and reactions of organopotassium species under flow coexistence conditions.

Electron-transfer-mediated generation of organometallic intermediates in the presence of electrophiles remains a longstanding challenge because competing reduction pathways often suppress desired bond formation. Herein, we report a flow-enabled coexistence strategy for the generation and reaction of highly reactive organopotassium intermediates. We achieved reductive potassiation of chloromethyl thioethers in the presence of electrophiles, enabling direct generation and trapping of organopotassium intermediates under coexistence conditions. Comparative experiments revealed that the corresponding stepwise protocol afforded significantly lower efficiency, demonstrating the importance of the coexistence conditions. These results establish electron-transfer-mediated coexistence reactions as a practical strategy for the generation and reactions of highly reactive organopotassium intermediates.