Harnessing the ambiphilicity of silyl nitronates in a catalytic asymmetric approach to aliphatic ?3-amino acids

Abstract Nitronate anions, formally generated by ?-deprotonating the corresponding nitroalkanes, are highly nucleophilic and versatile intermediates in many carbon–carbon bond-forming reactions. In contrast, silyl nitronates ambiphilic react, at same carbon atom, with both electrophiles nucleophiles. However, while their nucleophilicity has been well exploited catalytic enantioselective reactions imines aldehydes, utilizing electrophilicity of asymmetric synthesis remained elusive. Here we report facile, efficient general reactivity readily available ketene acetals, catalysed Lewis-acidic confined silylium imidodiphosphorimidate catalysts. The products this reaction, so-called nitroso obtained excellent enantioselectivity can be easily converted into N -Boc-? 3 -amino acid esters a single step.