Enantioselective Nickel-Catalyzed Reductive Anti-Arylative Annulation of Alkyne-Tethered Malononitriles to Construct Quaternary Stereocenters

A nickel-catalyzed reductive desymmetrizing annulation of alkyne-tethered malononitriles and (hetero)aryl iodides is reported for the access of cyclohexenones containing an a-all-carbon quaternary stereocenter. The use of a nickel catalyst derived from an electron-rich phosphinooxazoline ligand combined with iron powder as a reductant is crucial to the success of this transformation.