Carbene-Catalyzed Direct O-Functionalization of Ketone: Atroposelective Access to Non-C₂-Symmetric Binaphthyls

Disclosed here is NHC-catalyzed direct intermolecular trapping of the ketone oxygen atom with the acyl azolium intermediate. The overall reaction is a dynamic kinetic resolution process that converts ketone to the corresponding enol ester with well-controlled axial chirality. Our reaction eventually affords non-C-2-symmetric binaphthyl derivatives with important applications, such as in the area of asymmetric catalysis.