Recent Advance in Radical-Mediated Functionalization of Alkenes via Dual C—H Bond Conversion

doi:10.6023/cjoc202512049

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (4): 1440-1463.DOI: 10.6023/cjoc202512049 Previous Articles Next Articles

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自由基介导双C—H键转化的烯烃官能团化反应研究进展

于琛^a, 李宁^a, 薛琦^a, 李杨^a^,^*(), 汪苇航^b^,^*(), 李金恒^a^,^c^,^*()

^a 青岛科技大学化工学院青岛 266042
^b 中南大学湘雅二医院感染科湖南省病毒性肝炎临床医学研究中心湖南省病毒性肝炎临床医学研究中心长沙 410011
^c 河南师范大学化学化工学院新乡 453007

收稿日期:2025-01-31 修回日期:2026-02-04 发布日期:2026-03-06
通讯作者: 李杨, 汪苇航, 李金恒
基金资助:
国家自然科学基金(22001108); 国家自然科学基金(22271245); 江西省科技计划项目(20243BCE51084); 江西省科技计划项目(20242BAB25126); 山东省泰山学者建设工程专项(tsqn202408199); 河南师范大学化学化工学院开放研究基金(2021ZD01)

Recent Advance in Radical-Mediated Functionalization of Alkenes via Dual C—H Bond Conversion

Chen Yu^a, Ning Li^a, Qi Xue^a, Yang Li^a^,^*(), Weihang Wang^b^,^*(), Jinheng Li^a^,^c^,^*()

^a College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042
^b Clinical Research Center for Viral Hepatitis in Hunan Province, Department of Infectious Diseases, The Second Xiangya Hospital of Central South University, Central South University, Changsha 410011
^c School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007

Received:2025-01-31 Revised:2026-02-04 Published:2026-03-06
Contact: Yang Li, Weihang Wang, Jinheng Li
Supported by:
National Natural Science Foundation of China(22001108); National Natural Science Foundation of China(22271245); Jiangxi Provincial Science and Technology Project(20243BCE51084); Jiangxi Provincial Science and Technology Project(20242BAB25126); Taishan Scholars Construction Projects of Shandong Province(tsqn202408199); Open Research Fund of School of Chemistry and Chemical Engineering, Henan Normal University(2021ZD01)

As a fundamental structural unit of organic compounds, the direct transformation of C—H bond has long been one of the core research topics in organic chemistry. These radical reactions exhibit significant advantages in transformation of C—H bond due to their high reactivity and excellent functional group tolerance, attracting extensive attention from chemists. In particular, the radical-mediated functionalization of alkenes via dual C—H bond conversion has undergone rapid development and emerged as a powerful tool for the efficient construction of complex molecules. Herein, the recent advance in radical- mediated functionalization of alkenes via dual C—H bond conversion is summarized, categorized by three distinct pathways of C(sp³)—H/C(sp²)—H, C(sp²)—H/C(sp²)—H and C(sp³)—H/C(sp³)—H transformations. Reaction mechanisms and substrate scope are highlighted, and the future application potential of this research area is further discussed and prospected.

Key words: radical, alkene, C—H bond, alkene difunctionalization

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Chen Yu, Ning Li, Qi Xue, Yang Li, Weihang Wang, Jinheng Li. Recent Advance in Radical-Mediated Functionalization of Alkenes via Dual C—H Bond Conversion[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1440-1463.

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Fig. & Tab. 27

Scheme 1. Fe-catalyzed oxidative 1,2-alkylarylation of alkenes

Scheme 2. Lewis acid-catalyzed cascade cyclization reaction of N-arylacrylamides

Scheme 3. Alkylarylation reaction of activated alkenes with simple alkanes

Scheme 4. Visible-light-induced direct synthesis of alkylated oxindoles

Scheme 5. Photocatalyzed hydroxyalkyl radical cyclization reaction

Scheme 6. Cascade radical alkylation/cyclization for synthesis of 3,3-dialkyl substituted oxindoles

Scheme 7. Formylarylation of alkenes with O-containing alkanes via 1,2-difunctionalization

Scheme 8. Hydrogen atom transfer (HAT)-enabled tandem cyclization reaction

Scheme 9. Electrocatalytic alkylarylation-cyclization reaction with CH₂Cl₂

Scheme 10. Electrochemical annulation of N-arylacrylamides with γ,σ-unsaturated malonates

Scheme 11. Tandem addition/cyclization reaction of alcohols with N-acryloylbenzamides

Scheme 12. Radical-cascade alkylation/cyclization of N-acryloylbenzamides benzamides with alkanes via photoinduced LAILs-LMCT

Scheme 13. Oxidative alkylarylation of alkenes via dual C—H bond cleavage

Scheme 14. Redox-neutral alkene difunctionalization via benzylic C—H functionalization

Scheme 15. Multicomponent coupling C(sp³)—H/C(sp²)—H bond functionalization of alkenes

Scheme 16. Electrochemical alkylarylation of alkenes via C(sp3)—H/C(sp2)—H functionalization

Scheme 17. Transition-metal-catalyzed diarylation of styrenes

Scheme 18. Difunctionalization with electron-rich aromatic hydrocar bons

Scheme 19. Aldehyde-involved dual C(sp²)—H bond cascade cyclization reaction

Scheme 20. Transition-metal catalyzed cascade reactions of using N-aryklacrylamide as one of reactants

Scheme 21. Dual C(sp²)—H cascade cyclization reaction involving activated alkenes and aromatic aldehydes

Scheme 22. Difunctionalization of acrylamide with aldehyde in a cascade process

Scheme 23. Cascade cyclization of alkenes with aromatic/aliphatic aldehydes

Scheme 24. 1,2-Dialkylation of alkenes with two distinct C(sp3)—H bonds

Scheme 25. Organoelectrocatalysis enables direct cyclopropanation of alkenes

Scheme 26. Electrochemically mediated intermolecular cyclopropanation of unactivated alkenes

Scheme 27. Transformation of light alkanes and asymmetric dicarbofunctionalization of alkenes.

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自由基介导双C—H键转化的烯烃官能团化反应研究进展

Recent Advance in Radical-Mediated Functionalization of Alkenes via Dual C—H Bond Conversion

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