Progress in the Study of α-Functionalization of Enaminone

doi:10.6023/cjoc202207027

Abstract

Enaminones are versatile and extremely useful building blocks in organic synthesis with the advantages of easy availability, convenient storage, and distinct reactivity. In particular, such compounds are important precursors in heterocyclic chemistry. Recently, transition-metal-catalyzed or transition-metal-free α-functionalization of enaminones by C-H activation has emerged as a more atom- and step-economical strategy for the construction of functionalized enaminones or various heterocycles, and it has attracted the attention of many organic chemists. This review is divided into five sections based on the varied chemical bonds: C-C bond formation, C-O bond formation, C-N bond formation, C-X bond formation, and C-S/Se bond formation. The recent progress in functionalization of enaminone based on the reaction mechanism, reaction system, the scope of substrates, etc. is systematically reviewed.

Key words: enaminone, functionalization, coupling reaction, hypervalent iodine

Cite this article

Ning Liu, Xiaodan Cuan, Hui Li, Xiyan Duan. Progress in the Study of α-Functionalization of Enaminone[J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 602-621.

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Fig. & Tab. 39

Scheme 1. General structure and application of enaminones

Scheme 2. Dehydrogenative alkenylation reaction of cyclic enaminones

Scheme 3. Synthesis of 3-vinyl chromones via the reactions between o-hydroxyphenyl enaminones and alkenes

Scheme 4. Palladium-catalyzed C(sp2)-H activation with enaminones and alkenes for pyrrole synthesis

Scheme 5. Cyclobenzylation of o-hydroxyarylenaminones with benzyl bromide

Scheme 6. Gold-catalyzed alkynylation/cyclization of o-hydr- oxyarylenaminones

Scheme 7. Oxidative cyclization of N-aryl enaminones

Scheme 8. Palladium-catalyzed oxidative cyclization of N-aryl enaminones

Scheme 9. PIDA catalyzed oxidative cyclization of N-aryl enaminones

Scheme 10. Palladium-catalyzed oxidative cyclization of tertiary enamines

Scheme 11. Transient and recyclable halogenation coupling of o-hydroxyphenyl enaminones and aryl boronic acids

Scheme 12. Palladium(II)-catalyzed direct arylation of enaminones

Scheme 13. Cyclic reaction of enamine and nitrile

Scheme 14. Palladium-catalyzed oxidative coupling reactions of (Z)-enamines with isocyanides

Scheme 15. Trifluoromethylation of enaminones with trifluoromethane sulfinate

Scheme 16. Visible-light-driven trifluoromethylation of enaminones

Scheme 17. Togni reagent-mediated trifluoromethylation of enaminone

Scheme 18. C-H Trifluoromethylation and chromone annulation of enaminones

Scheme 19. C-O coupling reaction of enamines and carboxylic acid catalyzed by PhIO

Scheme 20. Highly site-selective metal-free C-H acyloxylation of tertiary enaminones

Scheme 21. Thermoinduced free-radical C-H acyloxylation of tertiary enaminones

Scheme 22. PhIO-mediated trifluoroethoxylation and azirination of enamines

Scheme 23. Direct oxidative coupling of enaminone and electron-deficient amines

Scheme 24. Iodine(III)-mediated oxidative cross-coupling of enaminone and propargylamines

Scheme 25. Toward C2-nitrogenated chromones by N-hetero- arylation of enaminones

Scheme 26. NBS-promoted C-H amination of enaminones

Scheme 27. Toward C2-nitrogenated chromones by N-heteroarylation of enaminones

Scheme 28. Halogenation of tertiary enaminone

Scheme 29. Fluorination of enaminone

Scheme 30. Electrochemical C-H halogenations of enaminones with sodium halide (NaX) as halogen source

Scheme 31. KIO3 catalyzed thiolation reaction of enaminones

Scheme 32. Synthesis of disulfide-functionalized enaminones and 1,4-thiazines via the reactions of enaminones and β-amino- ethanethiol

Scheme 33. Synthesis of disulfide-functionalized enaminones and 1,4-thiazines via the reactions of enaminones and β-aminoethanethiol

Scheme 34. Synthesis of pyrazole by domino C-H sulfonylation of enaminones

Scheme 35. K2S2O8 oxidized the thiocyanation of enaminone

Scheme 36. PIDA mediated the thiocyanation of enaminone

Scheme 37. Visible light-induced thiocyanation of enaminone

Scheme 38. NBS promoted the thiocyanation of enaminone

Scheme 39. Copper-catalyzed thioalkynylation of thiocyanates with terminal alkynes

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