Research Progress in Radical-Mediated 1,n-Nitrogen Migration Reactions

doi:10.6023/cjoc202512013

Abstract

The radical-mediated 1,n-nitrogen migration reaction represents a novel strategy for skeleton rearrangement that enables the efficient intramolecular relocation of nitrogen-containing functional groups. As such, it has attracted considerable attention for the precise synthesis of high-value nitrogen-containing compounds. This review summarizes three types of nitrogen migration reactions classified by the migration site, including 1,2-nitrogen migration, 1,3-nitrogen migration, and remote nitrogen migration, along with their applications in organic synthesis. Furthermore, prospects for future development in this field are discussed.

Key words: radical, nitrogen migration, rearrangement, asymmetric migration

Cite this article

Jiahao Chen, Beibei Zhan, Xiaheng Zhang. Research Progress in Radical-Mediated 1,n-Nitrogen Migration Reactions[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1560-1571.

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Fig. & Tab. 22

Scheme 1. Radical-mediated 1,n-nitrogen migration

Scheme 2. Radical-mediated 1,2-nitrogen migration

Scheme 3. Copper-catalyzed 1,2-nitrogen migration for a-amino acetals synthesis

Scheme 4. Copper-catalyzed trifluoromethylation/1,2-nitrogen migration cascade reaction

Scheme 5. Copper-catalyzed oxidative cyclization/1,2-nitrogen migration cascade reaction

Scheme 6. Nickel/diboron cooperative catalysis for the synthesis of β-amino acid esters via 1,2-nitrogen migration

Scheme 7. Nickel-catalyzed BCBs ring-opening/1,2-nitrogen migration cascade reaction

Scheme 8. Visible-light-induced biomimetic 1,2-nitrogen migration

Scheme 9. Nickel-catalyzed asymmetric cross-coupling/1,2-nitrogen migration cascade reaction

Scheme 10. Copper-catalyzed 1,3-nitrogen migration for indole synthesis

Scheme 11. Ru or Fe-catalyzed enantioselective 1,3-nitrogen migration to access chiral α-amino acids

Scheme 12. Nonheme Fe 1,3-nitrogen migration for asymmetric chiral α-amino acids synthesis

Scheme 13. Radical-mediated 1,4-nitrogen migration

Scheme 14. Radical 1,4/5-nitrogen migration access to β(γ)-amino ketones via EDA strategy

Scheme 15. Radical decarboxylative 1,2,3-trifunctionalization of 3-enoic acids via 1,4-nitrogen migration

Scheme 16. Radical three-component reaction for the synthesis of β-amino sulfones via 1,4-nitrogen migration

Scheme 17. Visible-light-induced N-α C(sp3)—H amination of N-alkyl benzamides

Scheme 18. Ru-catalyzed enantioselective 1,6-nitrogen migration to access chiral γ-aminomethyl-γ-lactones

Scheme 19. Remote C(sp3)—H azidation of sulfamoyl azides via 1,6-nitrogen migration

Scheme 20. Visible-light-induced carboamination/1,4-nitrogen migration cascade reaction

Scheme 21. EnT-enabled 1,4-nitrogen migration for epoxide synthesis

Scheme 22. Visible-light-induced alkylamination/1,5-nitrogen migration cascade reaction

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自由基介导的1,n-氮迁移反应研究进展