Alkylation 7? - -NORPHOS

Norton and coworkers found that catalytic enantioselective hydrogenation of the C=N bond of iminium cations can be accomplished using a series of Ru complexes with chiral diphosphine ligands such as Chiraphos and Norphos [68], Even tetra-alkyl-substituted iminium cations can be hydrogenated by this method. These reactions were carried out with 2 mol.% Ru catalyst and 3.4—3.8 bar H2 at room temperature in CH2C12 solvent (Eq. (39)). 

Enantioselective Hydrosilylation of C=N Double Bonds in Ketoximes and Ketimines. Homogeneous enantioselective hydrosilylation of prochiral alkyl aryl ketoximes has been carried out by using a Rh-(R,R)-NORPHOS catalyst. Thus, hydrosilylation of r-butyl phenyl ketoxime in the presence of [Rh(COD)Cl]2-(R,R)-NORPHOS followed by aqueous acidic work-up afforded the corresponding amine (eq 3) [16.5% ee, (5)], which became inverted to 15.0% ee (R) when this reaction was performed in the presence of added ammonium hexafluo-rophosphate (RhiNHaPF = 1.1, CH2CI2 solvent). ... 

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