Electrochemical Decarboxylative Alkylation of Vinyl Azides Enabled by a Water‐Assisted Proton‐Coupled Electron Transfer Mechanism

Ketone derivatives are pivotal intermediates in pharmaceutical synthesis, yet conventional syntheses often rely on metals, high temperatures, and prolonged reaction times. Herein, we report a metal‐ and oxidant‐free electrochemical decarboxylative coupling of alkyl carboxylic acids with vinyl azides. The reaction proceeds sustainably in aqueous acetonitrile through a proton‐coupled electron transfer, generating NH imines that undergo in situ hydrolysis to afford ketones. The concise synthesis of Fenbufen exemplifies the green character of this radical‐based transformation.