Truly Catalytic and Enantioselective Pinacol Coupling of Aryl Aldehydes Mediated by Chiral Ti(III) Complexes^†

Abstract

A variety of chiral Ti(IV) complexes were reduced in situ with zinc in acetonitrile. The resulting chiral Ti(III) complexes were found to catalyze the pinacol coupling reaction stereoselectively. The best results were obtained from the Ti-SALEN complex, which was found to be an efficient catalyst at 10 mol % concentration. Various aromatic aldehydes were coupled to obtain chiral hydrobenzoin derivatives with high diastereoselectivity and enantioselectivity. A plausible mechanism is proposed that rationalizes the stereochemical outcome of the reaction.