incorporate fluxional groups provide enhanced selectivity in asymmetric transformations? To address this issue, we have designed chiral 4‐dimethylaminopyridine (DMAP) catalysts with fluxional chirality. These catalysts were found to be efficient in promoting the acylative kineticresolution of secondary alcohols and axially chiral biaryl compounds with selectivityfactors of up to 37 and 51, respectively.
hydrogenolysis of aryl triflates through desymmetrization and kinetic resolution that allows the facile construction of axially chiral biaryl scaffolds with excellent results. These chiral compounds could be further converted into chiral monophosphine ligands, which were then used in asymmetric allylicalkylation to produce the desired product with high regio- and enantioselectivities.