Recent Progress in Transition Metal Catalyzed C(sp3)—H Nitrene Insertion Reactions Assisted by Directing Groups

doi:10.6023/cjoc202211041

Abstract

The transition metal catalyzed activation of C(sp³)—H bonds to form carbon-nitrogen bonds has been a challenging and hot research area. The transition metal-catalyzed C(sp³)—H amination strategy provides a more direct and efficient way to form C—N bonds. With the vigorous development in the field of C—H bond activation, a variety of directing groups and transition metal catalyst systems have been developed, which provide effective tools for C(sp³)—H amination through the inner sphere mechanism. In recent years, important progress has been made in directing group-assisted C(sp³)—H bond amination reactions, and many catalyst systems based on different transition metals with cheap and efficient amination reagents have been developed. The research progress of transition metal-catalyzed C(sp³)—H nitrene insertion reaction assisted by directing groups in the past decade is reviewed.

Key words: directing group, nitrene insertion, transition metal, C(sp³)—H, C—N bond formation

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Xing Yang, Xu Liu, Lijia Wang. Recent Progress in Transition Metal Catalyzed C(sp³)—H Nitrene Insertion Reactions Assisted by Directing Groups[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 914-923.

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Fig. & Tab. 23

Scheme 1. Mechanism types of transition metal-catalyzed C(sp3)—H amination reactions

Scheme 2. Rhodium-catalyzed C(sp3)–H amination directed by oxime

Scheme 3. Iridium-catalyzed C(sp3)—H amination directed by oxime

Scheme 4. Cobalt-catalyzed C(sp3)—H amination directed by quinolone

Scheme 5. Rhodium-catalyzed asymmetric C(sp3)—H amination directed by quinoline

Scheme 6. Rhodium-catalyzed asymmetric C(sp3)—H amination directed by pyridine

Scheme 7. Cobalt-catalyzed C(sp3)—H amination directed by thioamides

Scheme 8. Cobalt-catalyzed asymmetric C(sp3)—H amination directed by thioamides

Scheme 9. Rhodium-catalyzed C(sp3)—H amination directed by dithiane

Scheme 10. Iridium-catalyzed C(sp3)—H amination directed by 2-acylimidazoles

Scheme 11. Ni-catalyzed C(sp3)—H amination directed by thioether

Scheme 12. Iridium-catalyzed C(sp3)—H amination involving TsN3 directed by oxime

Scheme 13. Iridium-catalyzed C(sp3)—H amination involving TrocN3 directed by oxime

Scheme 14. Rhodium/iridium-catalyzed C(sp3)—H amination directed by pyridine

Scheme 15. Ni-catalyzed C(sp3)—H amination directed by quinoline-amide

Scheme 16. Iridium-catalyzed C(sp3)–H amination promoted by pyridine-amide

Scheme 17. Rhodium-catalyzed C(sp3)—H amination directed by pyridine

Scheme 18. Rhodium-catalyzed asymmetric C(sp3)—H amination directed by oxime

Scheme 19. Rhodium-catalyzed C(sp3)—H amination directed by pyrazole-amide

Scheme 20. Palladium-catalyzed C(sp3)—H amination directed by oxime

Scheme 21. Rhodium-catalyzed C(sp3)—H amination directed by pyridine

Scheme 22. Rhodium-catalyzed C(sp3)—H amination directed by pyridine with anthranils

Scheme 23. Cobalt-catalyzed C(sp3)—H amination directed by thioamide involving anthranils

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导向基辅助的过渡金属催化C(sp³)—H键氮宾插入反应研究进展

Recent Progress in Transition Metal Catalyzed C(sp³)—H Nitrene Insertion Reactions Assisted by Directing Groups

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导向基辅助的过渡金属催化C(sp3)—H键氮宾插入反应研究进展