A practical and highly enantioselective non-enzymatic kinetic resolution of racemic aldols through enantioselective dehydration process was developed using a cation-binding Song’s oligoEG catalyst and using KF as the base. A wide range of racemic aldols were resolved with extremely high selectivity factors (s = up to 1,535) under mild reaction conditions. This protocol is easily scalable and provides an alternative approach for the syntheses of diverse biologically and pharmaceutically relevant chiral aldols in enantiomerically pure form. The extremely high selectivity factors achieved can be ascribed to systematic cooperative hydrogen-bonding catalysis in a densely confined chiral space, which mimics the action of enzymes. |