Efficient Electrochemistry for the Regioselective Preparation of (Hetero)aryl Halides with Lithium Halides as Halogen Sources

Abstract Aryl halides are pivotal intermediates in cross-coupling reactions and drug synthesis, yet traditional halogenation protocols suffer from toxic halogenating reagents, low atom economy, and poor regioselectivity for inert (hetero)arenes. Herein, we report an efficient, green, and regioselective electrocatalytic strategy for the direct C–H halogenation of (hetero)arenes using cost-effective lithium halides as the sole halogen sources. Conducted in an undivided cell, this protocol couples anodic electrophile generation with cathodic hydrogen evolution, entirely circumventing the need for chemical oxidants. The method exhibits a remarkably broad substrate scope, accommodating over ten distinct classes of heteroarenes, diverse anilines, phenols, and complex bioactive molecules with excellent chemoselectivity. Furthermore, the practical utility of this approach is demonstrated by seamless scalability, continuous-flow synthesis, and late-stage functionalization, ultimately providing a sustainable and robust platform for applications in modern drug discovery and green organic synthesis.