Advances in Selective Allylic C—H Amination of Internal Olefins

doi:10.6023/cjoc202407007

Abstract

In recent years, the allylic C—H amination of internal olefins has undergone rapid development. This reaction introduces nitrogen sources into the allylic positions of internal olefins via C—H activation efficiently to form new C—N bonds, thereby synthesizing nitrogen-containing compounds with significant biological activity and pharmaceutical potential. Given the relatively low reactivity of internal olefins and the challenges of chemoselectivity, regioselectivity and stereoselectivity during the reaction, the allylic C—H amination of internal olefins has been a great challenge for organic chemists. This review primarily covers the selective allylic C—H amination of internal olefins in recent years, categorizing the methods based on the mechanism of distinguishing different allylic C—H bonds to achieve selective amination, and summarizes the research progress in this field and its potential applications in synthesizing biologically active molecules.

Key words: internal olefin, allylic, amination

Cite this article

Yuan She, Shuyu Zhang, Le Wang. Advances in Selective Allylic C—H Amination of Internal Olefins[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 531-545.

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Fig. & Tab. 34

Scheme 1. Common allylic C—H amination reactions

Scheme 2. Cp*IrIII-catalyzed intermolecular allylic C—H amination

Scheme 3. Substrate scope expansion for Cp*IrIII-catalyzed intermolecular allylic C—H amination

Scheme 4. Mechanistic study of Cp*IrIII-catalyzed intermolecular allylic C—H amination

Scheme 5. A planar chiral rhodium indenyl catalyst for selective allylic C—H amination

Scheme 6. Substrate scope expansion for the chiral rhodium indenyl catalyst for selective allylic C—H amination

Scheme 7. Mechanism of chiral indenyl-rhodium-catalyzed allylic C—H amination reaction

Scheme 8. Predicting selective C—H amination using the difference in 1JCH (Δ1JCH)

Scheme 9. Substrate scope expansion of 1,1-disubstituted and internal olefin compounds

Scheme 10. Allylic C—H amination reaction of vinylsilanes and vinylboronates

Scheme 11. Substrate scope expansion for the allylic C—H amination reaction targeting vinylsilanes and vinylboronates

Scheme 12. Catalytic cycle mechanism for the allylic C—H amination reaction of vinylsilanes and vinylboronates

Scheme 13. Intermolecular C—H amination of allylsilanes promoted by the β-silicon effect

Scheme 14. Substrate scope expansion for intermolecular C—H amination of allylsilanes promoted by the β-silicon effect

Scheme 15. Mechanism of intermolecular C—H amination of allylsilanes promoted by the β-silicon effect

Scheme 16. B(MIDA) directed selective allylic/propargylic C—H amination reaction

Scheme 17. Substrate scope expansion for B(MIDA) directed allylic selective C—H amination reaction

Scheme 18. Mechanistic study of B(MIDA) directed allylic selective C—H amination reaction

Scheme 19. 8-Aminoquinoline directed allylic C—H amination of inactivated internal olefins

Scheme 20. Substrate scope expansion for 8-aminoquinoline directed allylic C—H amination of inactivated internal olefins

Scheme 21. Plausible mechanism for 8-aminoquinoline directed allylic C—H amination of inactivated internal olefins

Scheme 22. Sustainable manganese catalyst [MnIII(ClPc)] for late-stage selective allylic C—H amination

Scheme 23. Substrate scope expansion for sustainable manganese catalyst [MnIII(ClPc)] for late-stage selective C—H amination

Scheme 24. Mechanism of allylic selective C—H amination reaction with sustainable manganese catalyst [MnIII(ClPc)]

Scheme 25. Influence of steric and stereoelectronic differences on amination sites with sustainable manganese catalyst

Scheme 26. Rhodium(II)-catalyzed allylic 1,3-diamination reaction

Scheme 27. Substrate scope expansion for rhodium(II)-catalyzed allylic 1,3-diamination reaction

Scheme 28. Experimental investigation of rhodium(II)-catalyzed allylic 1,3-diamination mechanism

Scheme 29. Mechanism of rhodium(II)-catalyzed internal olefins allylic 1,3-diamination reaction

Scheme 30. Blue-light-induced Pd(0/I/II)-catalyzed allylic C—H amination

Scheme 31. Blue-light-induced Pd(0/I/II)-catalyzed allylic C—H amination process

Scheme 32. Potential side reactions and radical precursors optimization in Pd(0/I/II)-catalyzed allylic C—H amination

Scheme 33. Substrate scope expansion for blue-light-induced Pd(0/I/II)-catalyzed allylic C—H amination

Scheme 34. Blue-light-induced Pd(0/I/II)-catalyzed stereoselective C—H amination

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内烯烃烯丙基选择性C—H键胺化反应研究进展