Selective Three-Component Reductive Alkylalkenylation of Unbiased Alkenes via Carbonyl-Directed Nickel Catalysis

A Ni-catalyzed enantioselective reductive three-component alkylalkenylation of β,γ-alkenyl ketones with cis-alkenyl iodides and fluoroalkyl iodides in the presence of Mn is reported. By leveraging five-membered nickellacycles stabilized by pendant ketone group and chiral bis­(oxazoline) (BiOx) ligand, this three-component protocol allows efficient access to enantioenriched β-alkenyl ketones from simple starting materials. Ni-catalyzed three-component alkylalkenylation of diverse electronically unbiased alkenes beyond β,γ-alkenyl ketones that enables regioselective construction of two C­(sp3)–C­(sp3) and C­(sp3)–(sp2) bonds in one single operation is also demonstrated.