1,3‐Difunctionalization of Allyl Carboxylates Enabled by 1,2‐Radical Migration (RaM) and Ruthenium‐Catalyzed Remote C–H Activation

Radical migration, especially 1,2‐radical migration (1,2‐RaM), has emerged as a powerful strategy in reaction discovery and synthetic development, enabling highly selective 1,3‐difunctionalization of alkenes and granting access to previously unexplored functional molecules and chemical space, with broad implications for complex molecule construction and medicinal chemistry. Herein, we report efficient and regioselective catalytic methods that, for the first time, combine 1,2‐radical migration (1,2‐RaM) with ruthenium‐catalyzed remote C–H activation to achieve difunctionalization at the meta ‐position of aromatic C(sp 2 )–H bonds and the C3 position of aliphatic C(sp 3 )–H bonds. This transformation demonstrates broad functional group tolerance and scalability to gram‐scale synthesis, offering a novel approach for the construction of complex molecules.