N−C Axially Chiral Anilines: Electronic Effect on Barrier to Rotation and A Remote Proton Brake

Yumiko Iwasaki, Ryuichi Morisawa, Satoshi Yokojima, Hiroshi Hasegawa, Christian Roussel, Nicolas Vanthuyne, Elsa Caytan, Osamu Kitagawa

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4 Citations (Scopus)

Abstract

N-Aryl-N-methyl-2-tert-butyl-6-methylaniline derivatives exhibit a rotationally stable N−C axially chiral structure and the rotational barriers around an N−C chiral axis increased with the increase in electron-withdrawing character of para-substituent on the aryl group. X-ray crystal structural analysis and the DFT calculation suggested that the considerable change of the rotational barriers by the electron effect of para-substituents is due to the disappearance of resonance stabilization energy caused by the twisting of para-substituted phenyl group in the transition state. This structural property of the N−C axially chiral anilines was employed to reveal a new acid-decelerated molecular rotor caused by the protonation at the remote position (remote proton brake).

Original languageEnglish
Pages (from-to)4453-4458
Number of pages6
JournalChemistry - A European Journal
Volume24
Issue number17
DOIs
Publication statusPublished - 2018 Mar 20

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Keywords

  • amines
  • axial chirality
  • density functional calculations
  • electronic effect
  • proton brake

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Cite this

Iwasaki, Y., Morisawa, R., Yokojima, S., Hasegawa, H., Roussel, C., Vanthuyne, N., Caytan, E., & Kitagawa, O. (2018). N−C Axially Chiral Anilines: Electronic Effect on Barrier to Rotation and A Remote Proton Brake. Chemistry - A European Journal, 24(17), 4453-4458. https://doi.org/10.1002/chem.201706115