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

The highly enantioselective totally N-selective hydroxyamination reaction of -aryl--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 0.05mol% catalyst loading. The products could be easily transformed to useful -amino amides and 1,2-diamines. Besides, a possible transition state model was proposed to elucidate the origin of the chirality induction.