Electrochemical Borylation of Alkyl Halides: Fast, Scalable Access to Alkyl Boronic Esters

Herein, a fast, scalable, and transition-metal-free borylation of alkyl halides (X = I, Br, Cl) enabled by electroreduction is reported. This process provides an efficient and practical access to primary, secondary, and tertiary boronic esters at a high current. More than 70 examples, including the late-stage borylation of natural products and drug derivatives, are furnished at room temperature, thereby demonstrating the broad utility and functional-group tolerance of this protocol. Mechanistic studies disclosed that B₂cat₂ serves as both a reagent and a cathodic mediator, enabling electroreduction of difficult-to-reduce alkyl bromides or chlorides at a low potential.