Electrochemical oxidation induced highly selective three-component cross-coupling of diphenylphosphine

Multicomponent reactions (MCRs) offer an efficient alternative to multistep synthesis, yet achieving high selectivity without using excess reagents remains a longstanding challenge. Herein, we report a highly selective electrochemical oxidative three-component coupling of diphenylphosphine with elemental sulfur/selenium and diverse coupling partners. The metal- and external oxidant-free protocol proceeds efficiently using an equimolar (1:1:1) ratio of the three components, providing straightforward access to six classes of organophosphorus compounds. The method exhibits broad substrate scope and excellent functional-group compatibility, delivering 82 examples in good to excellent yields. Furthermore, the reaction proceeds under mild conditions with excellent chemoselectivity and can be readily performed on gram scale, highlighting its practicality and scalability. This work demonstrates the potential of electrochemical multicomponent coupling as a sustainable and efficient strategy for the synthesis of structurally diverse organophosphorus compounds.