{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Rummel L"],"funding":["Deutsche Forschungsgemeinschaft"],"pagination":["e202204393"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC9401023"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["61(29)"],"pubmed_abstract":["We present an experimental and computational study on the conformers of N,N'-diphenylthiourea substituted with different dispersion energy donor (DED) groups. While the unfolded anti-anti conformer is the most relevant for thiourea catalysis, intramolecular noncovalent interactions counterintuitively favor the folded syn-syn conformer, as evident from a combination of low-temperature nuclear magnetic resonance measurements and computations. In order to quantify the noncovalent interactions, we utilized local energy decomposition analysis and symmetry-adapted perturbation theory at the DLPNO-CCSD(T)/def2-TZVPP and sSAPT0/6-311G(d,p) levels of theory. Additionally, we applied a double-mutant cycle to experimentally study the effects of bulky substituents on the equilibria. We determined London dispersion as the key interaction that shifts the equilibria towards the syn-syn conformers. This preference is likely a factor why such thiourea derivatives can be poor catalysts."],"journal":["Angewandte Chemie (International ed. in English)"],"pubmed_title":["London Dispersion Favors Sterically Hindered Diarylthiourea Conformers in Solution."],"pmcid":["PMC9401023"],"funding_grant_id":["SPP 1807 (SCHR 597/27-2)"],"pubmed_authors":["Schreiner PR","Becker J","Hausmann H","Domanski MHJ","Rummel L"],"additional_accession":[]},"is_claimable":false,"name":"London Dispersion Favors Sterically Hindered Diarylthiourea Conformers in Solution.","description":"We present an experimental and computational study on the conformers of N,N'-diphenylthiourea substituted with different dispersion energy donor (DED) groups. While the unfolded anti-anti conformer is the most relevant for thiourea catalysis, intramolecular noncovalent interactions counterintuitively favor the folded syn-syn conformer, as evident from a combination of low-temperature nuclear magnetic resonance measurements and computations. In order to quantify the noncovalent interactions, we utilized local energy decomposition analysis and symmetry-adapted perturbation theory at the DLPNO-CCSD(T)/def2-TZVPP and sSAPT0/6-311G(d,p) levels of theory. Additionally, we applied a double-mutant cycle to experimentally study the effects of bulky substituents on the equilibria. We determined London dispersion as the key interaction that shifts the equilibria towards the syn-syn conformers. This preference is likely a factor why such thiourea derivatives can be poor catalysts.","dates":{"release":"2022-01-01T00:00:00Z","publication":"2022 Jul","modification":"2025-04-04T21:52:13.403Z","creation":"2025-04-04T21:52:13.403Z"},"accession":"S-EPMC9401023","cross_references":{"pubmed":["35544611"],"doi":["10.1002/anie.202204393"]}}