Efficient Catalytic Enantioselective Hydroxyamination of α-Aryl-α-Cyanoacetates with 2-Nitrosopyridines.

The highly enantioselective totally N-selective hydroxyamination reaction of α-aryl-α-cyanoacetates with 2-nitrosopyridines was realized by using a chiral N,N'-dioxide/Mg(OTf)2 complex as catalyst, which enriches the nitroso chemistry. A variety of 2-cyano-2-[hydroxyl(pyrydin-2-yl)amino]acetates with quaternary stereocenters and potential antibacterial activities were obtained in excellent yields with good to excellent ee values under as low as 0.05 mol % catalyst loading. The products could be easily transformed to useful α-amino amides and 1,2-diamines. Besides, a possible transition state model was proposed to elucidate the origin of the chirality induction.