Asymmetric Allylic C–H Alkylation via Palladium(II)/<i>cis</i>-ArSOX Catalysis

We report the development of Pd­(II)/cis-aryl sulfoxide-oxazoline (cis-ArSOX) catalysts for asymmetric C–H alkylation of terminal olefins with a variety of synthetically versatile nucleophiles. The modular, tunable, and oxidatively stable ArSOX scaffold is key to the unprecedented broad scope and high enantioselectivity (37 examples, avg. > 90% ee). Pd­(II)/cis-ArSOX is unique in its ability to effect high reactivity and catalyst-controlled diastereoselectivity on the alkylation of aliphatic olefins. We anticipate that this new chiral ligand class will find use in other transition metal catalyzed processes that operate under oxidative conditions.