Remarkable progress in the area of asymmetric organocatalysis has been achieved in the last decades. Cinchona alkaloids and their derivatives have emerged as powerful organocatalysts owing to their reactivities leading to high enantioselectivities. Cinchona alkaloids consist of pseudoenantiomeric pairs and induce high enantioselectivities in asymmetric processes. The asymmetric desymmetrization (AD) of meso-cyclic anhydrides catalyzed by pseudoenantiomeric pairs of cinchona alkaloids, quinine (QN) and quinidine (QD), has been investigated with Density Functional Theory (DFT) to understand the origins of the stereoselectivities in these reactions. The distortion-interaction model has been employed to rationalize the experimentally observed enantiomeric ratios. Predicted enantioselectivies have been found to be in accordance with experimental findings with the assistance of catalytic solvent molecules.