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.
| Identifer | oai:union.ndltd.org:kaust.edu.sa/oai:repository.kaust.edu.sa:10754/691643 |
| Date | 19 March 2023 |
| Creators | Alotaibi, Salha |
| Contributors | Huang, Kuo-Wei, Physical Science and Engineering (PSE) Division, Schwingenschlögl, Udo, Zhang, Huabin |
| Source Sets | King Abdullah University of Science and Technology |
| Language | English |
| Detected Language | English |
| Type | Thesis |
| Rights | 2024-05-11, At the time of archiving, the student author of this thesis opted to temporarily restrict access to it. The full text of this thesis will become available to the public after the expiration of the embargo on 2024-05-11. |
| Relation | N/A |
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