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

REVIEW

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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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

Cite this article

Hai-Tian Luo , Zhen Huan , Jin-Dong Yang , Jin-Pei Cheng . Substituent Effects in Modern Radical Chemistry[J]. Chinese Journal of Organic Chemistry, 0 : 0 . DOI: 10.6023/cjoc202605001

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