Tunable enantioselective electrocatalytic functionalization of unactivated alkenes.

The tunable enantioselective functionalization of alkene feedstocks represents a highly desirable yet predominantly unresolved tactic for generating high-value scaffolds. Herein, we report a tunable enantioselective electrolytic system for dehydrogenative allylation, dehydrogenative alkenylation, and hydroalkylation reactions with identical substrates to afford structurally diverse products. This success hinges on the rational design of the stereoselective coupling of an electrogenerated nickel-bound α-carbonyl radical species that can trap unactivated alkenes and engage in various subsequent radical termination processes to enable the intermolecular functionalization of unactivated alkenes. The mild reaction conditions and sustainable electrocatalytic radical platform guarantee excellent functional group tolerance and substrate compatibility with unactivated alkenes (63 examples, up to 98% e.e.), and the process evolves H₂ without the need for external chemical oxidants. The utility of this enantioselective electrolytic strategy is demonstrated by its application in the stereoselective formal synthesis of (S)-SYK inhibitor, signifying substantial progress in synthetic methods.