Recent Progress on the Difunctionalization Reaction of 1,3-Enynes

doi:10.6023/cjoc202502004

Abstract

1,3-Enynes are a class of organic molecules with both alkyl and alkenyl groups, which have unique structural properties and have been used as the basic units in a variety of reactions to obtain a variety of specialized molecular structures. Selective difunctionalization of 1,3-enynes is an attractive strategy for the construction of 1,3-diene-type compounds, alkyne-based compounds, aromatic heterocycles such as thiophenes and pyrroles, as well as multisubstituted allene derivatives. In recent years, various catalytic strategies for the difunctionalization of 1,3-enynes have been widely reported, however, challenges in controlling the chemo- and regioselective difunctionalization of 1,3-enynes persist. The 1,2-, 3,4-, and 1,4-difunctionalization reactions of 1,3-enynes in the last few years are summarized, and the directions of development in this field are prospected.

Key words: 1,3-enyne, difunctionalization, alkynyl compound, allene derivative, 1,3-diene

Cite this article

Lianglong Sun, Kai Sun. Recent Progress on the Difunctionalization Reaction of 1,3-Enynes[J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3655-3671.

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Fig. & Tab. 32

Scheme 1. Main types of difunctionalization of 1,3-enynes

Scheme 2. Copper/Di-tert-butyl peroxide-catalyzed 1,2-hydroxy and phosphorylation of 1,3-enynes

Scheme 3. Copper(I)-catalyzed asymmetric 1,3-dipole cycloadditions of 1,3-enynes

Scheme 4. Photo-, copper-catalyzed three-component radical cross-coupling reactions of 1,3-enynes

Scheme 5. Photoinduced chromium-catalyzed diastereoselective 1,2-dialkylation of 1,3-enynes

Scheme 6. Copper-catalyzed 1,2-difunctionalization of 1,3-enynes via nitroxide insertions

Scheme 7. Sulfur insertion reaction of 1,3-enynes involving trisulfur radical anion ($\text{SO}{{_{3}^{}}^{-\ \bullet }}$)

Scheme 8. Selective difluoromethyl sulfur/selenocyclization of 1,3-enynes

Scheme 9. Palladium-catalyzed 3,4-trans-selective boron cyanidation of 1,3-enynes

Scheme 10. Palladium-catalyzed 3,4-cis-carboboration of 1,3-enynes

Scheme 11. Palladium-catalyzed 3,4-cis-difunctionalization of 1,3-enynes

Scheme 12. Palladium-catalyzed 3,4-difunctionalization of 1,3-enynes with imines and adjacent vinyl groups

Scheme 13. Photo-/nickel-catalyzed 3,4-/1,4-arylation and sulfonylation of 1,3-enynes

Scheme 14. Copper-catalyzed 1,4-alkylarylation of 1,3-enynes

Scheme 15. Copper-/palladium-catalyzed 1,4-arylboration of 1,3-enynes

Scheme 16. Metal-free catalyzed 1,4-fluoroamination of 1,3- enynes

Scheme 17. Copper-catalyzed 1,4-enantioselective oxycyana- tion of 1,3-enynes

Scheme 18. Copper-catalyzed 1,4-bis(trifluoromethylation) of 1,3-enynes

Scheme 19. N-Heterocyclic carbene-catalyzed 1,4-alkylacylation of 1,3-enynes

Scheme 20. Copper-catalyzed 1,4-halogenated trifluoromethylation of 1,3-enynes

Scheme 21. Copper-catalyzed 1,4-selenosulfonylation of 1,3-enynes

Scheme 22. Palladium-catalyzed 1,4-carboxyaromatization of 1,3-enynes

Scheme 23. Photo-/chromium-catalyzed asymmetric 1,4-difunctionalization of 1,3-enynes

Scheme 24. Copper-catalyzed regioselective 1,4-sulfonyl cyanation of 1,3-enynes

Scheme 25. Photo-/copper-catalyzed trifluoromethylaminocyanation of 1,3-enynes

Scheme 26. Metal-free catalyzed regioselective 1,4-sulfonyl iodination of 1,3-enynes

Scheme 27. Cobalt-catalyzed 1,4-carboxy sulfonylation of 1,3- enynes

Scheme 28. Electrocatalytic regionally selective aryl alkylation, dialkylation and hydrogen (deuterium) alkylation of 1,3-enynes

Scheme 29. Photo-/nickel-catalyzed 1,4-arylalkylation of 1,3-enynes

Scheme 30. Photo-/copper-catalyzed 1,4-bis(trifluoromethylation) of 1,3-enynes

Scheme 31. Nickel/electrocatalyzed 1,4-difunctionalization of 1,3-enynes

Scheme 32. Palladium-catalyzed multicomponent trifluoromethyl carbonylation of 1,3-enynes

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