Electrochemical umpolung of C‐H nucleophiles bearing three electron‐withdrawing groups to trigger radical 1,2‐alkylarylations of allylic alcohols

Abstract The electrochemical catalyst‐free generation of carbon radicals bearing three electron‐withdrawing groups from the corresponding C−H nucleophiles remains unexplored. To this end, we report a direct electro‐oxidation strategy to access these electrophilic carbon radicals under catalyst‐free conditions. Enabled by this strategy, the radical 1,2‐alkylarylations of allylic alcohols was realized, affording β ‐quaternary ketones with high functional group compatibility. This protocol is operationally simple and also easy to scale up.