Transition-metal-free electrochemical cross-electrophile coupling of activated benzyl alcohols and primary alkyl bromides

Cross-electrophile coupling (XEC) has emerged as a powerful strategy for constructing carbon─carbon bonds. Here, we report the first transition-metal-free electrochemical XEC between readily available benzyl alcohol derivatives and primary alkyl bromides, enabling the efficient construction of C(sp³)─C(sp³) bonds to access valuable benzylic quaternary and tertiary carbon centers. This method expands the reaction profiles of both benzyl alcohols and electrochemistry. A key to unlocking this transformation is the identification of 4-<i>tert</i>-butylbenzoyl (TBBz) as an effective activating group for benzyl alcohols. This modular protocol features broad substrate scope, compatibility with CO₂ and chlorosilanes as coupling partners, and is amenable to gram-scale synthesis. The synthetic utility of this method is exemplified by the simplified synthesis of high-value commercial building blocks and advanced intermediates for bioactive compounds, as well as the facile access to bioisosteric analogs of drug molecules.