Branch- and Enantioselective Allylic C−H Alkylation Works Well for Almost All Types of α-Alkenes

Abstract Asymmetric functionalization of alkenes represents one of the most attractive and straightforward methods to achieve precise assembly of molecular complexity from cost-effectiveness and sustainability viewpoints. Although the regio- and enantioselective transformations on the carbon-carbon double bond of alkenes have been extensively studied, those on the allylic C−H bonds of inactivated alkenes remain to be explored. Here, we report a Pd-catalyzed branch- and enantioselective allylic C−H alkylation, capable of accommodating almost all types of α-alkenes that range from feedstocks annually manufactured on million-ton scale to olefins tethering a wide scope of appended functionalities, providing unconventional access to chiral γ,δ-unsaturated amides. Notably, mechanistic studies reveal that the regioselectivity is not only governed by the coordination pattern of nucleophiles but also regulated by the ligational behaviors of ligands, highlighting the importance of the mono-ligation of chiral phosphoramidite ligands in provoking high levels of stereo- and branch-selectivity via a nucleophile-coordination enabled inner-sphere allylation pathway.