Palladium-Catalyzed Regiocontrollable Reductive Heck Reaction of Unactivated Aliphatic Alkenes

A general Pd-catalyzed intermolecular reductive Heck reaction of both terminal and internal unactivated aliphatic alkenes has been first developed. This method affords gamma- and delta-arylated alkyl carboxylic acid derivatives in high yields with complete anti-Markovnikov selectivity. Notably, the coupling process is stereoretentive for the alkyl chain. Mechanistically, alkyl palladacycle intermediates stabilized by directing group and ligand, hydride species multigenerated from PS/TFA reductant, are two key factors that successfully promote the reaction and regioselectivity.