Merging Aerobic Oxidation and Enamine Catalysis in the Asymmetric α-Amination of β-Ketocarbonyls Using N-Hydroxycarbamates as Nitrogen Sources

We describe herein an unprecedented asymmetric alpha-amination of beta-ketocarbonyls under aerobic conditions. The process is enabled by a simple chiral primary amine through the coupling of a catalytic enamine ester intermediate and a nitrosocarbonyl (generated in situ) derived from N-hydroxycarbamate. The reaction features high chemoselectivity and excellent enantioselectivity for a broad range of substrates.