Enantioselective addition of secondary phosphines to methacrylonitrile: catalysis and mechanism.

A highly enantioselective intermolecular hydrophosphination reaction is described. The (Pigiphos)nickel(II)-catalyzed reaction of secondary phosphines and methacrylonitrile gives chiral 2-cyanopropylphosphines in good yield and high enantiomeric excess (ee's up to 94%; (R)-(S)-Pigiphos = bis[(R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl}cyclohexylphos phine). We propose a mechanism involving coordination of methacrylonitrile to the dicationic nickel catalyst followed by 1,4-addition of the phosphine, and then, rate-determining proton transfer. This mechanism is supported by (a) the experimentally determined rate law (rate = k'[Ni][methacrylonitrile][t-Bu(2)PH]), (b) a large primary deuterium isotope effect k(H)/k(D) = 4.6(1) for the addition of t-Bu(2)PH(D) at 28.3 degrees C in toluene-d(8), (c) the isolation and characterization of the species Ni(kappa(3)-Pigiphos)(kappaN-methacrylonitrile), and (d) DFT calculations of model compounds.