现代自由基化学中的取代基效应

doi:10.6023/cjoc202605001

有机化学 ›› 2026, Vol. 46 ›› Issue (9): 3317-3327.DOI: 10.6023/cjoc202605001 上一篇下一篇

综述与进展

现代自由基化学中的取代基效应

罗海天^a, 桓臻^a, 杨金东^a^,^*(), 程津培^a^,^b^,^c

^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化学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 发布日期:2026-08-28
作者简介:
^† 共同第一作者
基金资助:
国家自然科学基金(22571181); 国家自然科学基金(22193011); 国家自然科学基金(22393891); 以及海河实验室资助项目.

Substituent Effects in Modern Radical Chemistry

Hai-Tian Luo^a, Zhen Huan^a, Jin-Dong Yang^a^,^*(), Jin-Pei Cheng^a^,^b^,^c

^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

Received:2026-05-01 Revised:2026-07-27 Published:2026-08-28
Contact:
^* E-mail: jdyang@mail.tsinghua.edu.cn
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
^† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22571181); National Natural Science Foundation of China(22193011); National Natural Science Foundation of China(22393891); Haihe Laboratory of Sustainable Chemical Transformations

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摘要/Abstract

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

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 patterns revealed by these parameters, and representative examples of their application in probing reaction mechanisms.

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

引用此文

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, 2026, 46(9): 3317-3327.

Hai-Tian Luo, Zhen Huan, Jin-Dong Yang, Jin-Pei Cheng. Substituent Effects in Modern Radical Chemistry[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3317-3327.

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图/表 16

图1. 取代三氟苯乙烯的热环化二聚反应

Figure 1. Thermal cycloaddition reaction of substituted trifluorostyrenes

Substituent	σ_mb	σ_JJ^•	Substituent	σ_mb	σ_JJ^•
H	0	0	p-Br	0.13	0.23
p-NMe₂	－0.96	1.00	p-Cl	0.11	0.22
p-CF=CF₂	0.40	0.86	p-CH=CH₂	0.03
p-SMe	－0.18	0.62	p-Me	－0.29	0.15
p-COMe	0.56	0.54	p-Et		0.15
p-SOMe	0.19	0.50	p-CF₃	0.49	－0.01
p-Ph	0.06	0.47	p-F	－0.24	－0.02
p-CN	0.86	0.42	m-Me	－0.20	0
p-COOH	0.31	0.38	m-Br	0.36	0.12
p-CONH₂	0.10	0.38	m-^tBu	－0.20	0.11
p-SO₂Me	0.64	0.41	m-CN	0.89	0.11
p-NO₂	0.86	0.36	m-OMe	－0.11	0.10
p-OCOMe	－0.14	0.35	m-CO₂Me	0.21	0.10
p-CO₂Me	0.48	0.33	m-Et	－0.15
p-SiMe₃	0.14	0.31	m-F	0.23	0.03
p-^cPr	－0.31	0.29	m-NO₂	0.69	0.001
p-^tBu	－0.22	0.26	m-Cl	0.12	－0.05
p-OPh	－0.46		m-CF₃	0.39	－0.07
p-OMe	－0.77	0.23

表1. 基于取代三氟苯乙烯体系建立的σmb与σJJ•值

Table 1. σmb and σJJ• values established on substituted trifluo- rostyrenes system

图2. 通过瞬态吸收光谱测定对苯醌阴离子自由基2共轭酸的pKa

Figure 2. Measurement of pKa of semiquinone 2 with transient absorption spectroscopy

图3. 自由基活化的芳香亲核取代反应

Figure 3. SNAr of fluorophenols via homolysis-enabled electronic activation

图4. 基于C≡N振动频率计算的开壳层取代基及已知的闭壳层取代基的σm标度

Figure 4. σm constants of open-shell substituents calculated from their C≡N vibrational shifts plotted against those of closed-shell substituents

图5. 基于C≡N振动频率计算的开壳层取代基及已知的闭壳层取代基的σ＋标度

Figure 5. σ＋constants of open-shell substituents calculated from their C≡N vibrational shifts plotted against those of closed-shell substituents

图6. 开壳层取代基的分类

Figure 6. Classification of open-shell substituents

图7. 二氧合钌(VI)卟啉与烯烃的环氧化反应及其取代基效应研究

Figure 7. Alkene epoxidation by dioxoruthenium(VI) porphyrins and its substituents effect studies

图8. 双(对甲苯磺酰亚胺基)钌(VI)卟啉与烯烃的氮丙啶化反应及其取代基效应研究

Figure 8. Aziridination of alkenes by bis(tosylimido)ruthe- nium(VI) porphyrins and its substituent effects studies

图9. 双(亚胺基)钌(VI)卟啉与烯烃的氮丙啶化反应及其取代基效应研究

Figure 9. Aziridination of alkenes by bis(imido)ruthenium(VI) porphyrins and its substituent effects studies

图10. 铜催化烯烃氮丙啶化反应及其取代基效应研究

Figure 10. Copper catalyzed aziridination of alkenes and its substituent effects studies

图11. 阴离子M(II) (M=Mn, Fe, Co)络合物催化的烯烃氮丙啶化反应取代基效应研究

Figure 11. Substituent effects studies of anionic M(II) (M=Mn, Fe, Co) complexes catalyzed aziridination of alkenes

图12. 铜和银催化的烯烃氮丙啶化反应机理研究

Figure 12. Mechanistic studies of the copper- and silver-catalyzed olefin aziridination reactions

图13. CoIII(TAML)催化的烯烃氮丙啶化反应中C—N成键机制

Figure 13. Mechanism of C—N bond formation in CoIII(TAML) catalyzed aziridination reactions

图14. Fe(II)叶立德络合物与烯烃的亚烷基转移反应及其取代基效应研究

Figure 14. Alkylidene-transfer reaction of a Fe(II) ylide complex with alkenes and its substituent effects studies

图15. 钴(II)四苯基卟啉催化的卡宾转移反应取代基效应研究

Figure 15. Substituent effects studies of cobalt(II) tetraphenylporphyrin-catalysed carbene transfer reaction

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现代自由基化学中的取代基效应

Substituent Effects in Modern Radical Chemistry

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