Enantioselective catalytic radical decarbonylative azidation and cyanation of aldehydes.

ABSTRACT

Empowered by the ubiquity of carbonyl functional groups in organic compounds, decarbonylative functionalization was prevalent in the construction of complex molecules. Under this context, asymmetric decarbonylative functionalization has emerged as an efficient pathway to accessing chiral motifs. However, ablation of enantiomeric control in a conventional 2e transition metal-catalyzed process was notable because of harsh conditions (high temperatures, etc.) that are usually required. To address this challenge and use readily accessible aldehyde directly, we report the asymmetric radical decarbonylative azidation and cyanation. Diverse aldehydes were directly used as alkyl radical precursor, engaging in the subsequent inner-sphere or outer-sphere ligand transfer where functional motifs (CN and N3) could be incorporated in excellent site- and enantioselectivity. Mild conditions, broad scope, excellent regioselectivity (driven by polarity-matching strategy), and enantioselectivity were shown for both transformations. This radical decarbonylative strategy using aldehydes as alkyl radical precursor has offered a powerful reaction manifold in asymmetric radical transformations to construct functional motifs regio- and stereoselectively.