Dynamics of Meso–Chiral Interconversion in a Butterfly-Shape Overcrowded Alkene Rotor Tunable by Solvent Properties

Kalathil K. Kartha, Atsuro Takai, Zdeněk Futera, Jan Labuta, Masayuki Takeuchi

Research output: Contribution to journalArticlepeer-review

Abstract

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.

Original languageEnglish
Pages (from-to)16466-16471
Number of pages6
JournalAngewandte Chemie - International Edition
Volume60
Issue number30
DOIs
Publication statusPublished - 2021 Jul 19

Keywords

  • chirality
  • conformation analysis
  • crowded alkenes
  • diastereomers
  • solvent effects

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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