Palladium-Catalyzed para-Selective C–H Olefination and Acetoxylation of Benzylamines Enabled by an Unmasked Benzoyl Template

Benzylamines belong to an important class of building blocks in the synthesis of biologically active natural products and drugs. Encumbered by amide-directed ortho-C–H activation, remote para-selective C–H functionalization of benzylamines has hitherto not been realized to date. Here, we report a palladium-catalyzed para-selective C–H olefination and acetoxylation of benzylamines using a functionalized benzoyl template. Enhancing the coordination strength of the directing group in the template significantly improved the site selectivity of C–H functionalization.