Electrooxidation‐Induced C(sp3)–H/C(sp2)–H Radical‐Radical Cross‐Coupling between Xanthanes and Electron‐Rich Arenes

Comprehensive Summary The arylation of C(sp 3 ) − H bonds has been a priority research topic in organic synthesis. Minsici reactions have been the powerful methods for C(sp 3 ) − C(sp 2 ) bonds formation. Despite its mature development, the scopes of arenes are usually suitable for electron‐deficient heterocyclic compounds, rather than electron‐rich arenes. Herein, we report an electrooxidation‐induced alkylation of electron‐rich arenes with H 2 evolution under exogenous oxidant‐free conditions, avoiding the utilization of metal catalysts. This protocol is well performed with various electron‐rich aniline derivatives and nitrogen‐containing heterocyclic compounds. We anticipate that this electro‐oxidative C(sp 3 ) − H arylation represents an important expansion for the classic arenes alkylation, thereby proving an attractive strategy for the developments of radical cross‐coupling chemistry.