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 α-amination of β-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.