A chiral magnesium potassium binaphthyldisulfonate cluster, as a chiral Bronsted acid catalyst, was shown to catalyze an enantioselective cycloaddition of styrenes with aldimines for the first time. The strong Bronsted acidity of the catalyst precursors, which might dissolve drying agents and take up the leached Mg2+ and K+, serendipitously led to good enantioselectivity. Mechanistic aspects were supported by X-ray and ESI-MS analysis of the catalyst and a kinetics study of the reaction. Useful transformations to optically active 1,3-amino alcohols on a gram scale were also demonstrated.