Data-mining the diaryl(thio)urea conformational landscape: Understanding the contrasting behavior of ureas and thioureas with quantum chemistry
The conformations adopted by urea and thiourea functional groups influence catalysis and binding. We combine data-mining with quantum chemical calculations to understand the differences in conformational behavior for these two important structural motifs. We developed a Python tool to automate the c...
| Main Authors: | , , , , |
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| Format: | Journal article |
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Elsevier
2018
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| _version_ | 1797094121775562752 |
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| author | Luchini, G Ascough, D Alegre-Requena, J Gouverneur, V Paton, R |
| author_facet | Luchini, G Ascough, D Alegre-Requena, J Gouverneur, V Paton, R |
| author_sort | Luchini, G |
| collection | OXFORD |
| description | The conformations adopted by urea and thiourea functional groups influence catalysis and binding. We combine data-mining with quantum chemical calculations to understand the differences in conformational behavior for these two important structural motifs. We developed a Python tool to automate the compilation of X-ray structural information and perform conformational clustering and visualization, based on SMILES input. While diarylureas have an overwhelming preference for the anti,anti-conformer, diarylthioureas adopt a mixture of anti,anti- and anti,syn-conformers. Computations show the anti,anti-thiourea conformer is destabilized by out-of-plane rotations which avoid a steric clash with the sulfur atom. These conformational preferences were studied computationally under a variety of conditions, and apart from in the gas-phase, a preference for anti,anti-ureas was found. Consistent with experiments, this preference increases in more polar environments. Quantitative predicted ratios are sensitive to the computational treatment of solvation effects, with COSMO-RS giving more realistic amounts of the anti,anti-conformer in THF and DMSO. |
| first_indexed | 2024-03-07T04:09:45Z |
| format | Journal article |
| id | oxford-uuid:c76f51f9-27ea-4ea6-a3ee-a7d6af2047db |
| institution | University of Oxford |
| last_indexed | 2024-03-07T04:09:45Z |
| publishDate | 2018 |
| publisher | Elsevier |
| record_format | dspace |
| spelling | oxford-uuid:c76f51f9-27ea-4ea6-a3ee-a7d6af2047db2022-03-27T06:45:02ZData-mining the diaryl(thio)urea conformational landscape: Understanding the contrasting behavior of ureas and thioureas with quantum chemistryJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:c76f51f9-27ea-4ea6-a3ee-a7d6af2047dbSymplectic Elements at OxfordElsevier2018Luchini, GAscough, DAlegre-Requena, JGouverneur, VPaton, RThe conformations adopted by urea and thiourea functional groups influence catalysis and binding. We combine data-mining with quantum chemical calculations to understand the differences in conformational behavior for these two important structural motifs. We developed a Python tool to automate the compilation of X-ray structural information and perform conformational clustering and visualization, based on SMILES input. While diarylureas have an overwhelming preference for the anti,anti-conformer, diarylthioureas adopt a mixture of anti,anti- and anti,syn-conformers. Computations show the anti,anti-thiourea conformer is destabilized by out-of-plane rotations which avoid a steric clash with the sulfur atom. These conformational preferences were studied computationally under a variety of conditions, and apart from in the gas-phase, a preference for anti,anti-ureas was found. Consistent with experiments, this preference increases in more polar environments. Quantitative predicted ratios are sensitive to the computational treatment of solvation effects, with COSMO-RS giving more realistic amounts of the anti,anti-conformer in THF and DMSO. |
| spellingShingle | Luchini, G Ascough, D Alegre-Requena, J Gouverneur, V Paton, R Data-mining the diaryl(thio)urea conformational landscape: Understanding the contrasting behavior of ureas and thioureas with quantum chemistry |
| title | Data-mining the diaryl(thio)urea conformational landscape: Understanding the contrasting behavior of ureas and thioureas with quantum chemistry |
| title_full | Data-mining the diaryl(thio)urea conformational landscape: Understanding the contrasting behavior of ureas and thioureas with quantum chemistry |
| title_fullStr | Data-mining the diaryl(thio)urea conformational landscape: Understanding the contrasting behavior of ureas and thioureas with quantum chemistry |
| title_full_unstemmed | Data-mining the diaryl(thio)urea conformational landscape: Understanding the contrasting behavior of ureas and thioureas with quantum chemistry |
| title_short | Data-mining the diaryl(thio)urea conformational landscape: Understanding the contrasting behavior of ureas and thioureas with quantum chemistry |
| title_sort | data mining the diaryl thio urea conformational landscape understanding the contrasting behavior of ureas and thioureas with quantum chemistry |
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