Site‐Selective Pyridination of Benzylic and Allylic C−H bonds via Radical‐Radical Cross‐Coupling

Abstract Herein, we report a modular photocatalytic platform for the site‐selective pyridination of saturated hydrocarbon compounds employing organic photoredox catalysis to forge new carbon‐carbon bonds. The site‐selective C−H pyridination could couple benzylic/allylic C−H bonds with pyridylphosphonium salts, which installed directly and regioselectively from C−H heteroarenes through a radical‐radical cross coupling mechanism. This synthetic methodology could tolerate a variety of functional groups, complex heteroarenes, even late‐stage functionalization of pharmaceuticals selectively.