We developed an acylative desymmetrization of meso-1,2-diols using a binaphthyl-based N,N-4-dimethylaminopyridine (DMAP) derivative 1h with tert-alcohol substituents. The reaction proceeds with a wide range of acyclic meso-1,2-diols and six-membered-ring meso-1,2-diols to provide a monoacylate selectively with a high enantiomeric ratio (er). Only 0.1 mol % of the catalyst facilitated the reaction within a short reaction time (3 h) to afford enantio-enriched monoacylated products in moderate to good yield. Several control experiments revealed that the tert-alcohol units of catalyst 1h play a significant role in achieving high catalytic activity, chemoselectivity of monoacylation, and enantioselectivity.

Chiral N,N-4-(dimethylamino)pyridine (DMAP) derivatives, which can be readily prepared by the Ugi multicomponent reaction in a one-pot manner, have been efficiently applied to the enantioselective Steglich rearrangement of oxindole derivatives to give the desired products bearing a quaternary carbon center in high yield (>98% yield) and with high enantioselectivity (up to 99:1 er).

An efficient and simple protocol for the kinetic resolution of secondary alcohols is presented. The new system is based on a combination of chiral Brønsted acid, DABCO, and acetyl chloride and gives various enantioenriched alcohols with selectivity factors up to 105.

A highly efficient and improved method has been developed for Petasis reactions of various 2-pyridinecarbaldehydes with secondary amines and boronic acids under catalyst-free conditions. The desired products are obtained in up to 96% yield in refluxed acetonitrile.A highly efficient and improved method has been developed for Petasis reactions of various 2-pyridinecarbaldehydes with secondary amines and boronic acids under catalyst-free conditions.