Unsaturated Carboxylates as Electrophilic Synthons for Transition‐Metal‐Catalyst‐Free Electroreductive Deoxygenative Coupling

Abstract

ABSTRACT The use of ester‐derived electrophiles in transition‐metal‐free electroreductive C(sp 3 )─C(sp 3 ) bond formation remains largely unexplored. Herein, we report a sacrificial‐anode‐enabled electroreductive cross‐coupling of simple unsaturated carboxylates with unactivated alkyl halides. Aryl, alkenyl, and alkynyl carboxylates are readily incorporated, affording methylene‐bridged alkylarenes together with allylic and propargylic C(sp 3 )‐rich frameworks under mild conditions. Mechanistic studies support independent single‐electron reduction of both electrophilic partners, followed by radical‐radical coupling, alkoxide elimination, and cathodic deoxygenation via a Clemmensen‐like reduction pathway. This work establishes unsaturated carboxylates as a new class of alkylating reagents for electroreductive C(sp 3 )─C(sp 3 ) bond formation.