Recent Advances in the N-Aryl C—H Functionalization Using 7-Azaindole as Intrinsic Directing Group

doi:10.6023/cjoc202205034

Abstract

The intrinsic directing group is a functional group in the substrates and also serves as an essential component in products. Thus, the preinstallation and removal of directing groups are avoided. 7-Azaindole has been used as intrinsic directing group for the N-aryl-C—H functionalization of N-aryls under the catalysis of transition metals. Utilizing the C—H functionalization strategy, numerous functional groups were installed into the ortho-position of N-aryls of the corresponding N-aryl-7-azaindoles. In this review, the recent achievements on the transition-metal catalyzed N-aryl ortho-C—H functionalization directed by 7-azaindole are summarized.

Key words: 7-azaindole, intrinsic directing group, C—H activation, transition-metal catalyzed

Cite this article

Cheng Yuan, Changduo Pan. Recent Advances in the N-Aryl C—H Functionalization Using 7-Azaindole as Intrinsic Directing Group[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 156-170.

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Fig. & Tab. 34

Figure 1. Pharmaceuticals containing 7-azaindole motif

Figure 2. Transition-metal-catalyzed 7-azaindole-directed N-aryl C—H functionalization of N-aryl-7-azaindoles

Scheme 1. N-Aryl C—H alkenylation of N-aryl-7-azaindoles with vinyl acetates

Scheme 2. N-Aryl ortho-olefination of N-aryl-7-azaindoles

Scheme 3. N-Aryl C—H alkenylation of N-aryl-7-azaindoles with alkenes

Scheme 4. N-Aryl C—H alkenylation and annulation of N-aryl- 7-azaindoles

Scheme 5. N-Aryl C—H alkynylation of N-aryl-7-azaindoles with TIPS-EBX

Scheme 6. N-Aryl C—H alkylation of N-aryl-7-azaindoles with α-carbonyl sulfoxonium ylides

Scheme 7. N-Aryl C—H alkylation of N-aryl-7-azaindoles with α-diazotized Meldrum’s acid

Scheme 8. N-Aryl C—H alkylation of N-aryl-7-azaindoles with cyclopropanols

Scheme 9. C—H aminocarbonylation of N-aryl-7-azaindole with isocyanates

Scheme 10. N-Aryl C—H benzoylation of N-aryl-7-azaindole with α-keto acids

Scheme 11. N-Aryl C—H cyanation of N-aryl-7-azaindoles with NCTS

Scheme 12. Transformations of cyanated N-phenyl-7-azaindole

Scheme 13. C—H annulation of N-aryl-7-azaindoles with internal alkynes

Scheme 14. Annulation of N-aryl-7-azaindoles

Scheme 15. Annulation of N-aryl-7-azaindoles with electron-deficient olefins

Scheme 16. C—H annulation of N-aryl-7-azaindoles with alkenyl esters

Scheme 17. C—H alkylation and annulation of N-aryl-7-azaindoles with α,β-unsaturated ketones

Scheme 18. C—H annulation of N-aryl-7-azaindoles with diazo compounds

Scheme 19. N-Aryl C—H chlorination of N-aryl-7-azaindoles with DCE

Scheme 20. N-Aryl C—H acetoxylation of N-aryl-7-azaindoles with PhI(OAc)2

Scheme 21. N-Aryl C—H amidation of N-aryl-7-azaindoles with acyl azides

Scheme 22. Transformation of the amidated product into polycyclic heteroarenes

Scheme 23. N-Aryl C—H amidation of N-aryl-7-azaindoles with dioxazolones

Scheme 24. N-Aryl C—H phosphoramidation of N-aryl-7-azaindoles with phosphoryl azides

Scheme 25. C—N, C—O, C—Cl, C—S and C—Se bonds formation directed by 7-azaindole

Scheme 26. Synthetic applications of the imidated product

Scheme 27. N-Aryl amidation and aryoloxylation of N-aryl-7-azaindoles with N-aroyloxycarbomates

Scheme 28. N-Aryl C—H amination of N-aryl-7-azaindoles with anthranils

Scheme 29. Synthetic utility of ortho-aminated azaindoles

Scheme 30. N-Aryl C—H nitration of N-aryl-7-azaindoles with t-butyl nitrite.

Scheme 31. Rh(III)-catalyzed N-aryl C—H chalcogenation of N-aryl-7-azaindoles

Scheme 32. Cu(II)-catalyzed N-aryl C—H chalcogenation of N-aryl-7-azaindoles

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以7-氮杂吲哚为内在导向基团的N-芳基C—H官能化研究进展