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DOI: https://doi.org/10.6023/cjoc202605001

综述与进展

现代自由基化学中的取代基效应

  • 罗海天 ,
  • 桓臻 ,
  • 杨金东 ,
  • 程津培
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  • a清华大学化学系基础分子科学中心 北京 100084;
    b南开大学化学学院元素有机国家重点实验室 天津 300071;
    c物质绿色创造与制造海河实验室 天津 300192

收稿日期: 2026-05-01

  修回日期: 2026-07-27

  网络出版日期: 2026-08-28

基金资助

国家自然科学基金(Nos. 22222106, 21973052, 22193011, 21933008)以及海河实验室资助项目.

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Substituent Effects in Modern Radical Chemistry

  • Hai-Tian Luo ,
  • Zhen Huan ,
  • Jin-Dong Yang ,
  • Jin-Pei Cheng
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  • a Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084;
    b State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071;
    c Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192
#These two authors contributed equally.

Received date: 2026-05-01

  Revised date: 2026-07-27

  Online published: 2026-08-28

Supported by

National Natural Science Foundation of China (Nos. 22571181, 22193011, and 22393891) and the Haihe Laboratory of Sustainable Chemical Transformations

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摘要

取代基效应是建立分子结构与化学行为之间定量关系的重要工具. 经典的取代基参数多适用于极性分子, 对包含自旋离域作用的开壳层体系的电子效应描述能力有限. 近年来, 研究者陆续建立了针对有机自由基体系的取代基效应定量分析方法, 扩充了相关的参数标度, 为反应机理的解析和新反应的设计提供了有力手段. 本文从标度的建立及其在机理研究中的应用两个方面出发, 综述了近三十年来面向自由基化学的取代基效应研究代表性进展, 着重介绍标度建立的方法, 参数所蕴含的规律, 以及利用取代基效应分析反应机理的典型实例.

关键词： 取代基效应; 自由基化学; 线性自由能关系; 双参数模型; 反应机理

本文引用格式

罗海天 , 桓臻 , 杨金东 , 程津培 . 现代自由基化学中的取代基效应[J]. 有机化学, 0 : 0 . DOI: 10.6023/cjoc202605001

Abstract

Substituent effects constitute an essential tool for establishing quantitative relationships between molecular structure and chemical behavior. Classical substituent parameters are primarily applicable to polar molecular systems and exhibit limited capability in describing electronic effects in open-shell systems involving spin delocalization. In recent years, a variety of quantitative approaches to substituent effects have been developed for organic radical systems, leading to an expansion of the available parameter scales and providing powerful tools for mechanistic elucidation and the design of new reactions. This review surveys representative advances over the past three decades in the study of substituent effects in radical chemistry, focusing on both the development of substituent parameters and their applications in mechanistic investigations. Particular emphasis is placed on the methodologies for parameter establishment, the underlying pattern that parameters reveal, and representative examples of their use in probing reaction mechanisms.

Key words： substituent effects; radical chemistry; linear free energy relationships; dual-parameter model; reaction mechanisms

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