Photoinduced Nitrogen-to-Alkyl Radical Relay Heck Reaction of o -Alkylbenzamides with Vinyl Arenes by Palladium Catalysis.

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.