Recent Advances in Dicarbofunctionalization of Alkynes via Photoredox Catalysis

doi:10.6023/cjoc202512019

Abstract

Photoredox-catalyzed dicarbofunctionalization of alkynes has emerged as a cutting-edge research direction in organic synthesis. This strategy ingeniously integrates the mild activation capabilities of photochemistry with the efficient bond-forming characteristics of transition metal catalysis. Through mechanisms such as single-electron transfer, energy transfer, or proton-coupled electron transfer, highly selective dicarbofunctionalization of alkynes can be achieved under visible light conditions. Compared with traditional methods, this approach not only offers mild reaction conditions and excellent functional group tolerance, but also enables precise control over chemo-, regio-, and stereoselectivity, thereby providing a new paradigm for the efficient synthesis of polysubstituted alkenes, cyclic compounds, and bioactive molecules. This review systematically summarizes the latest advances in this field with a focus on the substrate scope, reaction mechanisms, strategies for selectivity control, and synthetic applications, while also offering perspectives on future development trends.

Key words: photoredox catalysis, transition metal catalysis, alkynes, regioselectivity, dicarbofunctionalization

Cite this article

Fu Ye, Weiming Yuan. Recent Advances in Dicarbofunctionalization of Alkynes via Photoredox Catalysis[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1146-1165.

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Fig. & Tab. 25

Scheme 1. Dicarbofunctionalization of alkynes via photoredox catalysis

Scheme 2. Dicarbofunctionalization of ketone acids and alkynes via photoredox catalysis

Scheme 3. Dicarbofunctionalization of ketone acids and acetylene via photoredox catalysis

Scheme 4. Synthesis of 6,5-benzospiroketal glycosides via photoredox-catalyzed radical addition/cyclization

Scheme 5. Photoredox-catalyzed dicyanation of alkynes

Scheme 6. Photoredox-catalyzed hydrogen atom transfer-enabled [3＋2] cycloaddition of aldehydes and alkynes for the synthesis of cyclopentanones

Scheme 7. Photoredox-catalyzed 1,2-dicarboxylation of unactivated alkynes with CO2

Scheme 8. Photoredox-catalyzed remote C(sp3)—H vinylation via a radical addition/translocation strategy

Scheme 9. Photoredox-catalyzed remote carboamination via vinyl radicals generated from alkynes with olefins/arenes

Scheme 10. Dicarbofunctionalization of unactivated alkynes via photoredox catalysis

Scheme 11. Mechanism of dicarbofunctionalization of unactivated alkynes via photoredox catalysis

Scheme 12. Alkyne pyridylcyanation via photoredox catalysis

Scheme 13. Mechanism of alkyne pyridylcyanation via photoredox catalysis

Scheme 14. Photoredox/nickel dual catalysis for cis-selective arylalkylation of alkynes

Scheme 15. Mechanism of photoredox/nickel dual catalysis for cis-selective arylalkylation of alkynes

Scheme 16. Photoredox/nickel dual catalysis for 1,2-carboallylation of alkynes

Scheme 17. Mechanism of photoredox/nickel dual catalysis for 1,2-carboallylation of alkynes

Scheme 18. Photoredox/nickel dual catalysis for acyl-alkylation of Alkynes

Scheme 19. Photoredox/nickel dual catalysis for intermolecular 1,2-carbocyanation of alkynes

Scheme 20. Photoredox/nickel dual catalysis for arylalkylation of alkynes

Scheme 21. Mechanism of photoredox/nickel dual catalysis for arylalkylation of alkynes

Scheme 22. Electrochemical/photochemical/nickel dual catalysis for stereodivergent synthesis of alkenes

Scheme 23. Photoredox/nickel dual catalysis for arylalkylation of acetylene

Scheme 24. Photoredox/copper-cocatalyzed anti-selective dicarbofunctionalization of terminal alkynes

Scheme 25. Photoredox/cobalt-cocatalyzed selective dicarbofunctionalization of alkynes

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