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

被引：30

作者：

Bisz, Elwira ^{[2
]}

Piontek, Aleksandara ^{[2
]}

Dziuk, Blazej ^{[2
]}

Szostak, Roman ^{[3
]}

Szostak, Michal ^{[1
,2
]}

机构：

[1] Opole Univ, Dept Chem, 48 Oleska St, PL-45052 Opole, Poland

[2] Univ Wroclaw, Dept Chem, F Joliot Curie 14, PL-50383 Wroclaw, Poland

[3] Rutgers State Univ, Dept Chem, 73 Warren St, Newark, NJ 07102 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2018年 / 83卷 / 06期

关键词：

BRIDGEHEAD BICYCLIC LACTAMS; HIGHLY TWISTED AMIDES; STEREOCHEMICAL INFORMATION; REACTIVITY; CHEMISTRY; TETRAFLUOROBORATE; DESTABILIZATION; ISOMERIZATION; COMMUNICATION; SPECTROSCOPY;

D O I：

10.1021/acs.joc.8b00019

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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.

引用

页码：3159 / 3163

页数：5

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