One of the most influential characteristics of cinchona-based catalyst systems is their active conformation, because this decides the nature and extent of the stereoselectivity. The conformational space is rather small due to the rigidity and bulk of the substituents and gives rise to a restricted number of conformer populations. Wynberg and co-workers have done a Later, Bürgi and Baiker, through combined NMR experiments and ab initio calculations, revealed that the anti open conformation of the catalyst is the most stable in aprotic solvents. They also observed that in polar solvents, the syn closed and anti closed conformations were preferred over the anti open conformation. As the implicit solvents employed in the current computational study are dichloromethane and dichloroethane, a systematic conformational analysis was required at the outset in order to identify the most stable conformer. In order to carry out such an analysis, it was necessary to identify the principal torsional angles that distinguish the conformers from each other. Cinchona catalysts are rigid molecules containing relatively few rotatable bonds, and torsional angles around rotatable single bonds in the vicinity of the two chiral carbon atoms, namely C8 and C9 (see Supplementary(SI) Fig. ), are crucial structural parameters of the conformational space. Four torsional angles, modelled as α (N1-C8-C9-C4′), β (∠C8-C9-C4′-C3′), γ (∠C8-C9-O10-C9″), and δ (∠C9-O10-C9″-C10″) were seen to be the most relevant in determining the four different conformations that were possible for the rigid structure, and altering them gave rise to the four conformers. All the four conformers were investigated to find the most stable structure. A similar approach has been followed by Wong and co-workers in their computational study of the asymmetric methanolysis of meso-cyclic anhydrides through oxyanion hole stabilization. It is also worth mentioning that BzCPD has a flexible benzyl moiety at C9-O. It was, therefore, necessary to obtain a potential energy surface scan along the dihedral (C8-C9-O10-C11) to find the most stable orientation of the C9-O-benzyl group in BzCPD.