The Most Twisted Acyclic Amides: Structures and Reactivity.
The Most Twisted Acyclic Amides: Structures and Reactivity.
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DOI：
10.1021/acs.orglett.8b03175
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发表时间：
2018-12
期刊：
影响因子：
5.2
通讯作者：
Chengwei Liu;Shicheng Shi;Yongmei Liu;Ruzhang Liu;R. Lalancette;R. Szostak;M. Szostak
中科院分区：
文献类型：
--
作者：
Chengwei Liu;Shicheng Shi;Yongmei Liu;Ruzhang Liu;R. Lalancette;R. Szostak;M. Szostak
The synthesis, crystal structures, and reactivity of the most twisted acyclic amides described to date are reported. Substitution at the nitrogen atom in simple benzamides with Ts and acyl or carbamate groups provides a unique way to achieve almost perpendicular twist in N-acyclic amides (τ = 77°, N = Ac; τ = 87°, N = Boc). The overlap between the Nlp and CO π* orbital is disrupted due to geometrical constraints around the N-substituents. The perpendicular acyclic twisted amides represent a transition state mimic of cis-trans peptide isomerization thus far only accessible by excessively twisted bridged lactams.
