Enantioselective Addition of Nitromethane to 2‑Acylpyridine N‑Oxides. Expanding the Generation of Quaternary Stereocenters with the Henry Reaction

The direct asymmetric Henry reaction with prochiral ketones, leading to tertiary nitroaldols, is an elusive reaction so far limited to a reduced number of reactive substrates such as trifluoromethyl ketones or α-keto carbonyl compounds. Expanding the scope of this important reaction, the direct asymmetric addition of nitromethane to 2-acylpyridine N-oxides catalyzed by a BOX-Cu­(II) complex to give the corresponding pyridine-derived tertiary nitroaldols having a quaternary stereogenic center with variable yields and good enantioselectivity, is described.