Dynamics of Meso-Chiral Interconversion in a Butterfly-Shape Overcrowded Alkene Rotor Tunable by Solvent Properties.
chirality
conformation analysis
crowded alkenes
diastereomers
solvent effects
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:
19 Jul 2021
19 Jul 2021
Historique:
revised:
15
04
2021
received:
23
02
2021
pubmed:
28
4
2021
medline:
28
4
2021
entrez:
27
4
2021
Statut:
ppublish
Résumé
Elucidation of dynamics of molecular rotational motion is an essential part and challenging area of research. We demonstrate reversible diastereomeric interconversion of a molecular rotor composed of overcrowded butterfly-shape alkene (FDF). Its inherent dual rotatory motion (two rotors, one stator) with interconversion between two diastereomers, chiral trans-FDF and meso cis-FDF forms, has been examined in detail upon varying temperatures and solvents. The free energy profile of 180° revolution of one rotor part has a bimodal shape with unevenly positioned maxima (transition states). FDF in aromatic solvents adopts preferentially meso cis-conformation, while in non-aromatic solvents a chiral trans-conformation is more abundant owing to the solvent interactions with peripheral hexyl chains (solvophobic effect). Moderate correlations between the trans-FDF/cis-FDF ratio and solvent parameters, such as refractive index, polarizability, and viscosity were found.
Identifiants
pubmed: 33905168
doi: 10.1002/anie.202102719
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
16466-16471Subventions
Organisme : Japan Society for the Promotion of Science
ID : 19K05229
Organisme : Ministry of Education, Culture, Sports, Science and Technology
ID : 26102009
Organisme : Ministry of Education, Culture, Sports, Science and Technology
ID : 15K21721
Organisme : Ministry of Education, Culture, Sports, Science and Technology
ID : JP20H05868
Informations de copyright
© 2021 Wiley-VCH GmbH.
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