Substituent Effects in Modern Radical Chemistry

doi:10.6023/cjoc202605001

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (9): 3317-3327.DOI: 10.6023/cjoc202605001 Previous Articles Next Articles

REVIEW

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
通讯作者: 杨金东
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: Jin-Dong Yang
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

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

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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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Fig. & Tab. 16

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

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

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

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

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

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

Figure 6. Classification of open-shell substituents

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

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

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

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

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

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

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

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

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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