title: Nickel(II)-catalyzed highly enantioselective hydrophosphination of methacrylonitrile.
abstract: 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.
authors.affiliation: Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Hönggerberg, CH-8093 Zürich, Switzerland.
authors.forename: Aaron D
authors.initials: AD
authors.lastname: Sadow
authors.forename: Isabelle
authors.initials: I
authors.lastname: Haller
authors.forename: Luca
authors.initials: L
authors.lastname: Fadini
authors.forename: Antonio
authors.initials: A
authors.lastname: Togni