Palladium-Catalyzed Regiodivergent Three Component Alkenylamination of Terminal Dienes with Alkyl and Aryl Amines

We report a palladium-catalyzed method for 4,3- or 4,1-selective alkenylamination of terminal dienes. Three component couplings proceed with alkenyl triflates and several amines, giving vicinal carboamination with a Xantphos-supported catalyst and distal difunctionalization with a phosphoramidite ligand. Experimental evidence indicates selectivity in the former reactions is largely influenced by the substrate whereas the latter is catalyst controlled, orchestrated by a key pi-stacking interaction among the ligand, solvent, and substrate.