Nickel(II)-catalyzed highly enantioselective hydrophosphination of methacrylonitrile

The dicationic Ni(II) complex Ni(Pigiphos)(THF)](ClO4)2, 1](ClO4)2 ((R)-(S)-Pigiphos = bis-{(R)-1-(S)-2-(diphenylphosphino)ferrocenyl]ethyl}cyclohexylphosphine), catalyzes the addition of bulky aliphatic secondary phosphines to methaacrylonitrile. This hydrophosphination reaction reaches TON = 900 and enantioselectivities up to 94%. A catalytic cycle involving 1,4-conjugate addition of R2PH to methacrylonitrile is supported by the isolation and characterization of a catalytically active N-coordinated, methacrylonitrile Ni complex.