A palladium-catalyzed aryl-to-alkyl radical relay Heck reaction of amides at α-C(sp3)-H sites with vinyl arenes is described. This process displays a broad substrate scope with respect to both amide and...

Here, a palladium-catalyzed photoinduced N-to-alkyl radical relay Heck reaction of o-alkylbenzamides at benzylic sites with vinyl arenes is described. The reaction employs neither exogeneous photosensitizers nor external oxidants. It is proposed to proceed via a N-to-alkyl hybrid palladium–radical mechanism which occurs under mild conditions that are compatible with a wide range of functional groups. The products are easily transformed to azepinone derivatives, which are prevalent in pharmaceuticals and natural products.

A palladium-catalyzed aryl-to-alkyl radical relay Heck reaction of amides at α-C(sp3)-H sites with vinyl arenes is described. This process displays a broad substrate scope with respect to both amide and alkene components and provides access to a diverse classes of more complex molecules. The reaction is proposed to proceed via a hybrid palladium-radical mechanism. The core of the strategy is the fast oxidative addition of aryl iodide and fast 1,5-HAT overcome the slow oxidative addition of alkyl halides, and photoexcitation effect suppress the undesired β-H elimination. It is anticipated that this approach would inspire the discovery of new palladium-catalyzed alkyl-heck methods.