A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling Reaction
The DFT calculations of the simplified model of the asymmetric Suzuki–Miyaura coupling reaction were performed at the M062x/LANL2DZ theory level at first. It was found that enantioselective reactions mediated by the palladium complexes of chiral C,P-ligands follow a four-stage mechanism similar to t...
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Wiley
2017-01-01
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| Series: | Journal of Chemistry |
| Online Access: | http://dx.doi.org/10.1155/2017/3617527 |
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| author | Radomir Jasiński Oleg M. Demchuk Dmytro Babyuk |
| author_facet | Radomir Jasiński Oleg M. Demchuk Dmytro Babyuk |
| author_sort | Radomir Jasiński |
| collection | DOAJ |
| description | The DFT calculations of the simplified model of the asymmetric Suzuki–Miyaura coupling reaction were performed at the M062x/LANL2DZ theory level at first. It was found that enantioselective reactions mediated by the palladium complexes of chiral C,P-ligands follow a four-stage mechanism similar to that proposed previously as one of the most credible mechanisms. It should be underlined that the presence of substituents in the substrates and the chiral ligand at ortho positions determines the energies of possible diastereoisomeric transition states and intermediates in initial reaction steps. This suggests that, in practice, a sharp selection of theoretically possible paths of chirality transfer from the catalyst to the product should have a place and, therefore, the absolute configuration of the formed atropisomeric product is defined and can be predicted. |
| format | Article |
| id | doaj-art-5ab69aeb443141439219bd0e785712a8 |
| institution | Kabale University |
| issn | 2090-9063 2090-9071 |
| language | English |
| publishDate | 2017-01-01 |
| publisher | Wiley |
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| series | Journal of Chemistry |
| spelling | doaj-art-5ab69aeb443141439219bd0e785712a82025-02-03T01:32:12ZengWileyJournal of Chemistry2090-90632090-90712017-01-01201710.1155/2017/36175273617527A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling ReactionRadomir Jasiński0Oleg M. Demchuk1Dmytro Babyuk2Institute of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, PolandDepartment of Organic Chemistry, Maria Curie-Skłodowska University, 33 Gliniana Street, 20-614 Lublin, PolandInstitute of Biology, Chemistry and Bioresources, Chernivtsi National University, 2 Kotsyubynsky Str., Chernivtsi 58012, UkraineThe DFT calculations of the simplified model of the asymmetric Suzuki–Miyaura coupling reaction were performed at the M062x/LANL2DZ theory level at first. It was found that enantioselective reactions mediated by the palladium complexes of chiral C,P-ligands follow a four-stage mechanism similar to that proposed previously as one of the most credible mechanisms. It should be underlined that the presence of substituents in the substrates and the chiral ligand at ortho positions determines the energies of possible diastereoisomeric transition states and intermediates in initial reaction steps. This suggests that, in practice, a sharp selection of theoretically possible paths of chirality transfer from the catalyst to the product should have a place and, therefore, the absolute configuration of the formed atropisomeric product is defined and can be predicted.http://dx.doi.org/10.1155/2017/3617527 |
| spellingShingle | Radomir Jasiński Oleg M. Demchuk Dmytro Babyuk A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling Reaction Journal of Chemistry |
| title | A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling Reaction |
| title_full | A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling Reaction |
| title_fullStr | A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling Reaction |
| title_full_unstemmed | A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling Reaction |
| title_short | A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki–Miyaura Cross-Coupling Reaction |
| title_sort | quantum chemical dft approach to elucidation of the chirality transfer mechanism of the enantioselective suzuki miyaura cross coupling reaction |
| url | http://dx.doi.org/10.1155/2017/3617527 |
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