N-C Axially Chiral Anilines: Electronic Effect on Barrier to Rotation and A Remote Proton Brake.
Chemistry
; 24(17): 4453-4458, 2018 Mar 20.
Article
em En
| MEDLINE
| ID: mdl-29363203
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).
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MEDLINE
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En
Ano de publicação:
2018
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Article