Organophotocatalytic Regioselective C−H Alkylation of Electron‐Rich Arenes Using Activated and Unactivated Alkenes

Abstract Direct alkylation of the C−H bond arenes in a selective manner is a long‐standing challenge. Herein, a metal‐free photocatalytic regioselective C−H alkylation method for electron‐rich arenes with both activated and unactivated alkenes was developed. The reaction tolerates a wide range of aromatic rings with diverse substitution patterns, as well as terminal and internal alkenes, providing a general and straightforward metal‐free method for C−C bond formation from inert C−H bonds. Moreover, alkynes are also compatible to give the C−H vinylation of electron‐rich arenes.