Reductive Dicarbofunctionalization of Unactivated Internal Alkenes via Iron Catalysis

We report an iron-catalyzed reductive fluoroalkylalkenylation of unactivated internal alkenes. Various fluoroalkyl bromides and the Togni reagent undergo this three-component coupling reaction smoothly, generating a diverse array of homoallylic fluoroalkanes with high efficiency. The method is notable for its ability to proceed without the need for directing or activating groups, offering excellent functional group tolerance, a broad substrate scope, and good applications in the late-stage difunctionalization of biorelevant molecules. Preliminary mechanistic studies suggest that fluoroalkyl radicals are involved in the catalytic cycle, which operates via a radical cascade addition pathway.