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

Research output: Contribution to journalArticle

2 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

Fingerprint

Aniline Compounds
Aniline
Brakes
Protons
Design for testability
Electrons
Protonation
Structural analysis
Structural properties
Stabilization
Rotors
Derivatives
X rays
Crystals
Acids

Keywords

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

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

N−C Axially Chiral Anilines : Electronic Effect on Barrier to Rotation and A Remote Proton Brake. / Iwasaki, Yumiko; Morisawa, Ryuichi; Yokojima, Satoshi; Hasegawa, Hiroshi; Roussel, Christian; Vanthuyne, Nicolas; Caytan, Elsa; Kitagawa, Osamu.

In: Chemistry - A European Journal, Vol. 24, No. 17, 20.03.2018, p. 4453-4458.

Research output: Contribution to journalArticle

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, vol. 24, no. 17, pp. 4453-4458. https://doi.org/10.1002/chem.201706115
Iwasaki Y, Morisawa R, Yokojima S, Hasegawa H, Roussel C, Vanthuyne N et al. N−C Axially Chiral Anilines: Electronic Effect on Barrier to Rotation and A Remote Proton Brake. Chemistry - A European Journal. 2018 Mar 20;24(17):4453-4458. https://doi.org/10.1002/chem.201706115
Iwasaki, Yumiko ; Morisawa, Ryuichi ; Yokojima, Satoshi ; Hasegawa, Hiroshi ; Roussel, Christian ; Vanthuyne, Nicolas ; Caytan, Elsa ; Kitagawa, Osamu. / N−C Axially Chiral Anilines : Electronic Effect on Barrier to Rotation and A Remote Proton Brake. In: Chemistry - A European Journal. 2018 ; Vol. 24, No. 17. pp. 4453-4458.
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AB - 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).

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