Recent Advances in Visible Light Photoredox-Catalyzed Alkynylation

doi:10.6023/cjoc202303020

Abstract

The synthesis and transformations of alkynes have held an important position in the field of organic synthesis. How to rapidly introduce alkynyl into organic molecules has been of great interest. Photoredox catalysis has been widely used in organic synthesis because it can generate high reactive free radical intermediates under mild conditions using green and clean energy. Visible light photocatalytic alkynylation has flourished in the last decade, which is believed to be a significant complement to the classic transition-metal-catalyzed Sonogashira reaction. This alkynylation could take place via in situ generated copper acetylide complex from terminal alkynes and copper, which also occurs through alkynyl radical species or radical addition elimination of non-terminal alkynes. Moreover, it was a good supplement to Sonogashira reaction that various radical precursors could be applied to alkynylation by visible-light photoredox catalysis. Based on the type of bonding of alkynylation, the research progress of alkynylation reactions by visible-light photoredox catalysis is reviewed, and the future development of this field is prospected.

Key words: alkynylation, radicals, photoredox, Sonogashira coupling

Cite this article

Chunming Gui, Tongyao Zhou, Haifeng Wang, Qiongjiao Yan, Wei Wang, Jin Huang, Fener Chen. Recent Advances in Visible Light Photoredox-Catalyzed Alkynylation[J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2647-2663.

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Fig. & Tab. 47

Figure 1. Alkyne-containing pharmaceuticals

Figure 2. Transformations of alkynes

Figure 3. Visible light photoredox-catalyzed alkynylation

Scheme 1. Activation of terminal alkynes by transition-metal copper

Scheme 2. Photoredox/copper dual-catalyzed asymmetric alkynylation of tetrahydroisoquinolines

Scheme 3. Photoredox/copper dual-catalyzed decarboxylative alkynylation of N-(acetoxy)phthalimides of α-amino acids

Scheme 4. Visible light-induced copper-catalyzed coupling of terminal alkynes and alkyl iodides

Scheme 5. Visible light-induced copper-catalyzed radical coupling reaction of cycloketone oxime esters, alkenes, and terminal alkynes

Scheme 6. Visible light-induced copper-catalyzed multicomponent coupling of arylamines, terminal alkynes and alcohols

Scheme 7. Visible light-induced copper-catalyzed decarboxylative alkynylation

Scheme 8. Copper-catalyzed enantioselective radical oxidative C(sp3)—H/C(sp)—H cross-coupling reaction with terminal alkynes

Scheme 9. Visible light-induced copper-catalyzed C(sp)—C(sp3) coupling of cycloketone oxime esters and terminal alkynes

Scheme 10. Visible light-induced copper-catalyzed difunctionalization of olefins

Scheme 11. Decarboxylative alkynylation of carboxylic acids with terminal alkynes using Cu/photoredox dual catalysis

Scheme 12. Visible light-induced copper-catalyzed alkynylation of remote unactivated C(sp3)—H bonds

Scheme 13. Radical multicomponent alkyl alkynylation of bicyclo[1.1.1]pentanes via synergistic photoredox and copper catalysis

Scheme 14. Photoredox-catalyzed trifluoromethylation of alkynes

Scheme 15. Photoredox-catalyzed cross-coupling reactions of arylalkynes with perfluoroalkyl iodides

Scheme 16. Photoredox-catalyzed alkynylation of EBX reagents

Scheme 17. Visible-light-induced chemoselective deboronative alkynylation

Scheme 18. Decarboxylative alkynylation of carboxylic acids using photoredox catalysis and EBX reagents

Scheme 19. Investigations of EBX reagents for radical alkynylations in photoredox catalysis

Scheme 20. Photoredox catalyzed C(sp3)—C(sp) coupling of dihydropyridines and EBX reagents

Scheme 21. Photoredox catalyzed functionalization of saturated O-heterocycles or alkenes and EBX reagents

Scheme 22. Photoredox catalyzed alkynylative ring-opening of cycloalkylamides

Scheme 23. Photomediated alkynylation and use of Ph-EBX reagents as photocatalyst

Scheme 24. Photoredox catalyzed remote C(sp3)—H alkynylation

Scheme 25. Photoexcitation of Ar-EBX for the alkynylation of cyclopropanes

Scheme 26. Gold catalyzed photoredox alkynylation of tetrahydroisoquinolines

Scheme 27. Gold catalyzed photoredox cross-coupling of tertiary α-silylamines with 1-iodoalkynes

Scheme 28. Visible-light-induced reductive decarboxylative C(sp3)—C(sp) bond coupling reaction

Scheme 29. Visible light-induced reductive alkynylation of aldehydes

Scheme 30. Visible light-mediated gold-catalyzed C(sp)—C(sp2) cross-coupling reaction

Scheme 31. Visible light-induced copper-catalyzed C(sp2)—C(sp) cross-coupling via aryl sulfonium salts

Scheme 32. Visible light-induced copper-catalyzed Sonogashira coupling of terminal alkynes and aryl halides

Scheme 33. Visible light-induced the synthesis of ynones, ynamides, and ynoates

Scheme 34. Photoredox mediated alkynylation of sp2 C(O)—H bonds

Scheme 35. Visible light-induced palladium-catalyzed dicarbofunctionalization of terminal alkynes

Scheme 36. Photoredox catalyzed radical alkynylation of α-phosphorus alcohols

Scheme 37. Visible light-induced copper-catalyzed direct C(sp)—P bond formation

Scheme 38. Visible-light-driven copper-catalyzed aerobic oxidative C(sp)—S coupling reaction

Scheme 39. Visible light-induced copper-catalyzed direct C(sp)—H/Si—H cross-coupling reaction

Scheme 40. Photoredox/copper co-catalyzed asymmetric propargylic radical cyanation

Scheme 41. Visible-light-mediated photocatalytic cross-coupling reaction of acetenyl ketones with benzyl trifluoroborate

Scheme 42. Photoredox/palladium co-catalyzed propargylic benzylation with propargylic carbonates

Scheme 43. Photoredox/chromium co-catalyzed radical carbonyl propargylation

Scheme 44. Visible light-induced homocoupling of propargyl bromides

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可见光氧化还原催化炔基化反应的研究进展