Fluoroalkylative Ketonization of Malononitrile-Tethered Alkenes via Nickel Electron-Shuttle and Lewis Acid Catalysis.

A binary Ni/Eu catalytic system has been developed, which enables an efficient reductive dicarbofunctionalization of unactivated alkenes with alkyl halides and malononitriles. The combination of Ni electron-shuttle catalysis with Eu(OTf), a non-redox-type Lewis acid, effectively activates the iminyl radicals, enabling the direct formation of the C(sp)-C(sp) bond and β-ketonitrile functionality across a variety of C═C double bonds. This reaction allows for the expedient synthesis of densely functionalized cyclic β-ketonitriles bearing all-carbon quaternary centers.