核磁共振氢谱中二苯基乙二胺衍生物手性识别其结构类似物

doi:10.11938/cjmr20182703

波谱学杂志 ›› 2019, Vol. 36 ›› Issue (4): 525-533.doi: 10.11938/cjmr20182703

核磁共振氢谱中二苯基乙二胺衍生物手性识别其结构类似物

杨盈², 黄少华^1,2, 冯继文³

1. 宁波大学新药技术研究院, 浙江宁波 315211;
2. 中国科学院青岛生物能源与过程研究所, 山东青岛 266101;
3. 波谱与原子分子物理国家重点实验室, 中国科学院武汉物理与数学研究所, 湖北武汉 430071

收稿日期:2018-12-19 出版日期:2019-12-05 发布日期:2019-02-26
通讯作者: 黄少华, 冯继文 E-mail:huangshaohua@nbu.edu.cn;jwfeng@wipm.ac.cn
基金资助:
the National Natural Science Foundation of China (21105108); the Key Technology Talent Program of Chinese Academy of Sciences (2015).

Mechanisms Underlying Enantiomeric Discrimination of Its Structural Analogues with a Diphenylethylenediamine Derivative Revealed by Proton NMR Spectroscopy

YANG Ying², HUANG Shao-hua^1,2, FENG Ji-wen³

1. Institute of Drug Discovery and Technology, Ningbo University, Ningbo 315211, China;
2. Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China;
3. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China

Received:2018-12-19 Online:2019-12-05 Published:2019-02-26
Supported by:
the National Natural Science Foundation of China (21105108); the Key Technology Talent Program of Chinese Academy of Sciences (2015).

1. 补充材料.pdf(112KB)

摘要/Abstract

摘要： 本文通过手性二苯基乙二胺与异氰酸酯的衍生化反应，合成了一种C₂对称的手性主体1.该主体可以手性识别其结构类似物：α-苯乙胺（客体2）、α-对甲氧基苯乙胺（客体9）以及它们的衍生物（客体3~8和10~13）.高分辨核磁共振氢谱（¹H NMR）显示了对映体识别中主客体间的氢键作用.结果表明，除含2个NO₂的客体7和12外，主体1可以较易识别含有两个伯胺的脲和酰胺衍生物.研究还发现，主体1对脲衍生物2、9比对酰胺衍生物有更强的氢键作用，此外主体1对（R）和（S）-脲衍生物中的CHCH₃基团也有更高的辨识能力.

关键词: 二苯基乙二胺, 衍生物, 对映体识别, 核磁共振(NMR)波谱

Abstract: A C₂-symmetric host (host 1) was synthesized by derivatization of chiral diphenylethylenediamine with phenylisocyanate. High-resolution proton nuclear magnetic resonance (¹H NMR) was used to investigate whether the chiral host could be used for enantiomeric discrimination of its structural analogues:α-phenylethylamine (guest 2), α-(p-methoxyphenyl)ethylamine (guest 9) and their derivatives (guests 3~8 and 10~13), and hydrogen-bonding interactions underlying the enantiomeric discrimination. It was observed that the host was able to recognize the urea and amide derivatives of the two primary amines, except for guests 7 and 12 bearing two NO₂ groups. The host had stronger hydrogen-bonding interactions with the urea derivatives of guests 2 and 9 than with the corresponding amide derivatives, and high enantiomeric discrimination ability for the CHCH₃ groups of the (R)- and (S)-urea derivatives.

Key words: diphenylethylenediamine, derivative, enantiomeric discrimination, nuclear magnetic resonance (NMR) spectroscopy

中图分类号:

O482.53

杨盈, 黄少华, 冯继文. 核磁共振氢谱中二苯基乙二胺衍生物手性识别其结构类似物[J]. 波谱学杂志, 2019, 36(4): 525-533.

YANG Ying, HUANG Shao-hua, FENG Ji-wen. Mechanisms Underlying Enantiomeric Discrimination of Its Structural Analogues with a Diphenylethylenediamine Derivative Revealed by Proton NMR Spectroscopy[J]. Chinese Journal of Magnetic Resonance, 2019, 36(4): 525-533.

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核磁共振氢谱中二苯基乙二胺衍生物手性识别其结构类似物

Mechanisms Underlying Enantiomeric Discrimination of Its Structural Analogues with a Diphenylethylenediamine Derivative Revealed by Proton NMR Spectroscopy

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