The facile synthesis of the stabilized axial and equatorial conformers of spiro-β-lactams was achieved via entrapment of cyclohexanone imines (Schiff bases) with acetoxyacetyl chloride in a [2 + 2]-cycloaddition reaction followed by their kinetic resolution. The immobilization of the racemic substrates on an inert solid support significantly reduced the reaction time and improved the enantioselectivity of conformers during kinetic resolution. The mechanism of the formation of the spiro-β-lactams was explored using B3LYP/6-31+G* level quantum chemical calculations.