从有机胺、有机膦、亚砜的构型翻转理解元素有机化合物结构的影响因素

doi:10.12461/PKU.DXHX202505012

大学化学 >> 2026, Vol. 41 >> Issue (7): 415-429.doi: 10.12461/PKU.DXHX202505012

师生笔谈上一篇

从有机胺、有机膦、亚砜的构型翻转理解元素有机化合物结构的影响因素

盛天祺¹, 杨雪楠¹, 李朝阳², 张韶光²

1 清华大学探微书院, 北京 100084;
2 清华大学化学系, 生命有机磷化学及化学生物学教育部重点实验室, 北京 100084

收稿日期:2025-05-08 录用日期:2025-07-31 发布日期:2026-06-27
通讯作者: 张韶光 E-mail:sgzhang@mail.tsinghua.edu.cn Shaoguang Zhang
基金资助:
国家自然科学基金(22101151);清华大学本科教育教学改革项目

Understanding structural influences in organoelement compounds through configurational inversion of amines, phosphines, and sulfoxides

Tianqi Sheng¹, Xuenan Yang¹, Zhaoyang Li², Shaoguang Zhang²

1 Tanwei College, Tsinghua University, Beijing 100084, China;
2 Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, China

Received:2025-05-08 Accepted:2025-07-31 Published:2026-06-27
Contact: Shaoguang Zhang E-mail:sgzhang@mail.tsinghua.edu.cn

摘要/Abstract

摘要： 氮(胺)、磷(膦)、硫(亚砜)中心手性化合物虽同为sp³杂化构型，但其构型翻转能垒和速率差异显著，导致手性异构体分离难度不同。本文以三者为例，系统探讨影响翻转能垒的核心因素，指出根本差异在于中心原子本身。这凸显“元素性质决定结构反应特性”的元素有机化学基本规律，旨在引导学生建立基于电子结构的理解路径。

关键词: 手性胺, 手性膦, 手性亚砜, 构型翻转, 元素有机化学

Abstract: Although nitrogen (amine), phosphorus (phosphine), and sulfur (sulfoxide) centered chiral compounds all adopt sp³-hybridized configurations, they demonstrate markedly different energy barriers and rates for configurational inversion, resulting in varying degrees of difficulty in chiral isomer separation. Using these three compound classes as representative examples, this study systematically examines the key factors governing inversion barriers. The analysis reveals that the fundamental distinction originates from the inherent properties of the central atoms, thereby illustrating the foundational principle of organoelement chemistry that “elemental characteristics determine structural and reactivity features”. This work aims to help students develop an electron structure-based approach for understanding structure-reactivity relationships.

Key words: Chiral amines, Chiral phosphines, Chiral sulfoxides, Configuration inversion, Organoelement chemistry

盛天祺, 杨雪楠, 李朝阳, 张韶光. 从有机胺、有机膦、亚砜的构型翻转理解元素有机化合物结构的影响因素[J]. 大学化学, 2026, 41(7): 415-429.

Tianqi Sheng, Xuenan Yang, Zhaoyang Li, Shaoguang Zhang. Understanding structural influences in organoelement compounds through configurational inversion of amines, phosphines, and sulfoxides[J]. University Chemistry, 2026, 41(7): 415-429.

链接本文: https://www.dxhx.pku.edu.cn/CN/10.12461/PKU.DXHX202505012

https://www.dxhx.pku.edu.cn/CN/Y2026/V41/I7/415

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从有机胺、有机膦、亚砜的构型翻转理解元素有机化合物结构的影响因素

Understanding structural influences in organoelement compounds through configurational inversion of amines, phosphines, and sulfoxides

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