Stereodivergent and enantiodivergent pathways for the Friedel–Crafts reactions were computationally studied with DFT methods. This study aims to explain recently observed solvent-dependent regioselectivity, and enantioselectivity when cinchona catalyst is used. Deprotonation reaction, Frontier Kohn-Sham orbitals, dual descriptors, Mulliken charges, and Hirshfeld atomic charge for reactant were calculated and analyzed. The most probable position of electrophilic attack and nucleophilic attack in-silico predicted aligns with experimental observations. The calculation of the transition states on the anionic and neutral model in a vacuum show preference for the electrophilic attack in the para position. In comparison to the anionic system, the presence of potassium cation improves ortho/para selectivity and increases the energy barrier. For the key enantioselective step, 12 transition states were calculated which covers 4 representative product such: (R)-ortho, (S)-ortho, (R)-para, and (S)-para. The computational study suggests, that the presence of the cesium cation is essential for the arrangement of the reactant and catalyst in the transition state, which leads to observed selectivity.