大学化学2024,Vol.39Issue(1) :111-118.DOI:10.3866/PKU.DXHX202306039

扭曲型酰胺——结构与功能

The Twisted Amides:Structures and Functions

史雷 詹梓烨 余志友
大学化学2024,Vol.39Issue(1) :111-118.DOI:10.3866/PKU.DXHX202306039

扭曲型酰胺——结构与功能

The Twisted Amides:Structures and Functions

史雷 1詹梓烨 1余志友1
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作者信息

  • 1. 哈尔滨工业大学(深圳)理学院,广东深圳 518055
  • 折叠

摘要

酰胺作为具有独特物理化学性质和生物活性的含氮化合物,其在医药、材料等领域已展现出了广泛的应用前景.与传统酰胺相比,扭曲型酰胺由于其分子内的p-TT共轭被不同程度地破坏,致使酰胺平面结构发生不同程度的扭曲,进而呈现出独特的反应活性.扭曲角τ和角锥化参数XN是衡量扭曲型酰胺扭曲程度的两个重要指标,τ描述了N—C(O)键的扭曲程度,XN则描述了氮原子的角锥化程度.τ=40°,XN=40°更是其在反应性上区别平面酰胺的关键阈值.本文着重介绍了当τ>40°,XN>40°时环状扭曲型酰胺和无环扭曲型酰胺的特殊结构与反应性能.

Abstract

Amides,as nitrogen-containing compounds with unique physicochemical properties and biological activities,have demonstrated broad application prospects in fields such as medicine and materials.Particularly,compared with the vast majority of traditional amides in which the intramolecular p-π conjugation effects lead to a planar structure,the twisted amides,however,present distortions of the amide bond from planarity,thus resulting conformational and electronic modifications such as amide bond twist and nitrogen pyramidalization.The bond distortion of twisted amide is typically defined by the Winkler-Dunitz distortion parameters twist angle(τ)and pyramidalization parameters(XN).The former describes the magnitude of rotation around the N—C(O)bond while the later describes pyramidalization at nitrogen and pyramidalization at carbon.The values of τ=40° and XN=40° are considered as threshold values that allow for unique reactivity of the twist amide bond.This article introduces the unique structure and reactivity of these compounds,focusing on cyclic twisted amides and acyclic twisted amides,based on the range of T>40° and XN>40°.

关键词

扭曲型酰胺/扭曲角/角锥化参数

Key words

Twisted amides/Twist angle/Pyramidalization parameter

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基金项目

哈尔滨工业大学(深圳)2021年度创新创业教育课程项目(INRP1023)

出版年

2024
大学化学
北京大学 中国化学会

大学化学

影响因子:0.636
ISSN:1000-8438
参考文献量35
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