Progress on Cobalt-Catalyzed C(sp2)—H Activation for the Construction of Nitrogen-Containing Benzo Heterocycles

doi:10.6023/cjoc202404038

Abstract

Nitrogen-containing benzo heterocycles serve as crucial scaffolds in natural products and biologically active molecules. In recent years, transition metal catalysis has emerged as a powerful strategy in C(sp²)—H activation, making significant contributions to the synthesis of nitrogen-containing benzo heterocycles. Embracing the concept of green and sustainable economy, the abundantly available cobalt metal is gaining attention as an economical catalyst among researchers. In this review, the research progress on cobalt-catalyzed C(sp²)—H activation for the construction of nitrogen-containing benzo heterocycles from 2015 to present is summarized. The cobalt catalysts used can be classified into cyclopentadienyl (Cp)-coordinated CpCo(III) catalysts as well as Cp-free Co(II) catalysts by species, and reaction types can be categorized into intermolecular and intramolecular reactions, which are systematically reviewed according to these classifications. Furthermore, the current limitations and future prospects of this field are summarized and discussed.

Key words: cobalt catalysts, C(sp²)—H activation, cyclization reactions, nitrogen-containing benzo heterocycles, transition metal catalysis

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Xun Tian, Guogang Deng, Xiaodong Yang. Progress on Cobalt-Catalyzed C(sp²)—H Activation for the Construction of Nitrogen-Containing Benzo Heterocycles[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 655-667.

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Fig. & Tab. 39

Figure 1. Natural products and pharmaceutical molecules containing nitrogen-containing benzo heterocyclic structures

Scheme 1. Mechanism of CpCo-catalyzed intermolecular C(sp2)—H activation for ring formation

Scheme 2. Multi-substituted isoquinolines synthesis from oximes and alkynes

Scheme 3. Multi-substituted quinolines synthesis from acylaniline and alkynes

Scheme 4. Indoles synthesis from aniline derivatives and alkynes

Scheme 5. Benzo-pyrimidines synthesis from imine substrates and dioxazolones

Scheme 6. Isoquinolinones synthesis from N-chlorobenzamide and alkynes

Scheme 7. Thiadiazine sulfoxides synthesis from benzenesulfo- nimides and dioxazolones

Scheme 8. Dihydroisoquinolines synthesis from benzimidates and vinylethylene carbonates

Scheme 9. Asymmetric synthesis of dihydroisoquinolinones from N-chlorobenzamide and olefins

Scheme 10. Indoloindolones synthesis from sulfoxonium ylides and anthranils

Scheme 11. Asymmetric synthesis of thiadiazine sulfoxides from benzenesulfonimides and dioxazolones

Scheme 12. 2-Acylindolines synthesis from aniline derivatives and acrylates

Scheme 13. Quinazolinones synthesis from primary amides and oxadiazolones

Scheme 14. Isoquinolinones synthesis from N-chlorobenza- mides and vinyl acetate

Scheme 15. 4-Silicon substituted dihydroisoquinolinones synthesis from N-chlorobenzamide and silicon substituted olefins

Scheme 16. Benzocyclic carbamates synthesis by intramolecular amidation from azidocarbonates

Scheme 17. Benzofused lactam synthesis by intramolecular amidation from dioxazolones

Scheme 18. Benzofused lactam synthesis by intramolecular amidation from dioxazolones

Scheme 19. Co(II)-catalyzed intermolecular ring-forming reactions through C(sp2)—H activation

Scheme 20. Base- and solvent-modulated regioselective synthesis of isoquinolinones and isoindolones

Scheme 21. Multicyclic lactams synthesis from formamides and ethylene/acetylene gas

Scheme 22. Multisubstituted isoquinolinones synthesis from benzamides and allenes

Scheme 23. 3-Iminoisoindolinones and phthalimides synthesis from benzoylhydrazine and isocyanides or carbon monoxide

Scheme 24. Isoquinolones/pyridinones synthesis from benza- mide/acrylamide and alkynes

Scheme 25. Isoquinolones/pyridinones synthesis from benza- mide/acrylamide and terminal alkynes

Scheme 26. Spirocycles synthesis from benzamides and maleimides

Scheme 27. Chemoselective spirocycles synthesis from benzamide and diazo compounds

Scheme 28. Naphthoimidazole synthesis from naphthylamines and hydroxylamine esters

Scheme 29. Facile and accessible synthesis of Salox* ligands

Scheme 30. Synthesis of P-stereo-genic hexacyclophosphamide by aryl phosphamides and alkynes

Scheme 31. Asymmetric synthesis of chiral dihydroisoquinolinones from benzamides and olefins

Scheme 32. Asymmetric synthesis of chiral nitrogen-containing heterocycles from benzamide/phosphoramidites and allenes

Scheme 33. Asymmetric synthesis of axially chiral isoquinoline derivatives from benzamide and alkynes/olefins

Scheme 34. Asymmetric synthesis of axially chiral isoquinolines/isoindolones derivatives by benzamide and allenes/olefins/ isocyanines

Scheme 35. Asymmetric synthesis of N-axially chiral benzolactosulfonamides from aryl sulfonamides and allenes/alkynes

Scheme 36. Enantioselective C—H/N—H cyclization of benzylamine derivatives with alkynes

Scheme 37. Asymmetric synthesis of N-axially chiral isoquinolinones by benzamides and alkynes

Scheme 38. Intramolecular synthesis of biaxial chiral polycyclic products from benzamides and alkynes

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钴催化C(sp²)—H活化构建苯并含氮杂环骨架的研究进展

Progress on Cobalt-Catalyzed C(sp²)—H Activation for the Construction of Nitrogen-Containing Benzo Heterocycles

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钴催化C(sp2)—H活化构建苯并含氮杂环骨架的研究进展