London Dispersion Favors Sterically Hindered Diarylthiourea Conformers in Solution.
Conformational Analysis
Local Energy Decomposition
Pauli Repulsion
Symmetry-Adapted-Perturbation Theory
σ-σ Interactions
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
18 07 2022
18 07 2022
Historique:
received:
24
03
2022
pubmed:
12
5
2022
medline:
14
7
2022
entrez:
11
5
2022
Statut:
ppublish
Résumé
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.
Identifiants
pubmed: 35544611
doi: 10.1002/anie.202204393
pmc: PMC9401023
doi:
Substances chimiques
Thiourea
GYV9AM2QAG
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202204393Informations de copyright
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
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