Electrooxidative Synthesis of Benzoin Bis‐Ethers From Alkynes and Alcohols

Herein, we present a mild and efficient electrochemical strategy for the synthesis of benzoin bis‐ethers via oxidative difunctionalization of alkynes. This protocol proceeds under ambient conditions without requiring transition‐metal catalysts or stoichiometric oxidants, utilizing electrons as a traceless redox mediator. The reaction exhibits broad substrate scope and excellent functional group tolerance. A gram‐scale experiments and product derivatization reactions highlight the practicality of this electrochemical strategy. Mechanistic investigations indicated a radical cation pathway, highlighting the utility of this sustainable approach for accessing valuable bis‐ether frameworks.