Barriers to Rotation in ortho-Substituted Tertiary Aromatic Amides: Effect of Chloro-Substitution on Resonance and Distortion

Planarity of the amide bond represents one of the most widely recognized properties of amides. Herein, we report a combined structural and computational study on the effect of ortho-substitution on resonance and barriers to rotation in tertiary aromatic amides. We demonstrate that ortho-chloro subst...

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Bibliographic Details
Published in:Journal of organic chemistry 2018-03, Vol.83 (6), p.3159-3163
Main Authors: Bisz, Elwira, Piontek, Aleksandara, Dziuk, Błażej, Szostak, Roman, Szostak, Michal
Format: Article
Language:English
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Summary:Planarity of the amide bond represents one of the most widely recognized properties of amides. Herein, we report a combined structural and computational study on the effect of ortho-substitution on resonance and barriers to rotation in tertiary aromatic amides. We demonstrate that ortho-chloro substitution in a class of benzamides that are important from the reactivity and medicinal chemistry perspective results in increased barriers to rotation around both the N–C­(O) and C–C­(O) axes. The effect of steric hindrance on structures, resonance energies, barriers to rotation, and proton affinities is discussed. The present study strongly supports the use of ortho-substitution in common benzamides to strengthen amidic resonance.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.8b00019