Bibenzyl compounds are widely found in natural products, and their derived dihydrostilbene derivatives exhibit excellent anti-tumor activity, serving as important lead structures in the field of drug research and development. However, existing synthetic methods mostly rely on noble metal catalysts and stoichiometric oxidizing/reducing agents, suffering from drawbacks such as cumbersome operations and limited applications. Based on the core concept of organic electrochemical synthesis that “uses electrons as green reagents”, this study develops a strategy for constructing bibenzyl compounds through electrochemical reductive coupling reaction, using naphthalene as the electron mediator, and cheap and readily available aryl halides and styrenes as raw materials. This strategy utilizes naphthalene to mediate the reductive dehalogenation of aryl halides at the cathode to generate phenyl radicals, which subsequently react with styrenes serving as radical acceptors. An electrochemical synthesis system without exogenous oxidizing/reducing agents and catalysts is thus developed. This system can efficiently prepare bibenzyl compounds under mild conditions, with excellent substrate applicability, being compatible with various aryl halides such as iodo-, bromo-, and chloro-substituted derivatives. It provides a new green and efficient synthetic pathway for bibenzyl compounds, and has good application potential in the field of drug synthesis.

Key words: halobenzene, organic electroreduction, C—C coupling, metal-free catalysis, naphthalene-mediated