Research Progress of Radical Reactions Involving Silyl Enol Ethers

doi:10.6023/cjoc202402007

Abstract

Due to the unique reactivity of silyl enol ethers, they have been widely employed in organic synthesis. As masked enol, they participate in classical reactions, such as Mukaiyama aldol reactions and Mukaiyama Michael additions, which can construct new C—C bonds. However, the synthesis of complex molecules often requires the utilization of novel and more efficient reaction pathways due to the limitations of ionic reactions. Silyl enol ethers exhibit excellent performance across various reaction systems involved in radical reactions. This article provides a comprehensive research summary of the synthesis of α-substituted carbonyl compounds and other functional organic molecules using silyl enol ethers as versatile and efficient reaction precursors which were reported in the past decade. The design of reactions and mechanisms was discussed by researchers under different reaction systems including photocatalysis, metal catalysis, metal-free reactions, and electrocatalysis, as well as the future prospect of this research topic.

Key words: silyl enol ether, radical reaction, α-carbonyl compound, transition metal

Cite this article

Zhaoyang Zhang, Weiwei Luo, Jun Zhou. Research Progress of Radical Reactions Involving Silyl Enol Ethers[J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2658-2681.

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Fig. & Tab. 46

Figure 1. Biologically active α-substitued carbonyl derivatives

Scheme 1. Photocatalytic synthesis of fluoroalkyl ketones from iodoalkanes and silyl enol ethers

Scheme 2. Synthesis of 3-fluoropyridine by photocatalytic one- pot method

Scheme 3. Synthesis of α-CF2CO2Me substituted compounds

Scheme 4. Synthesis of 1,4-dicarbonyl compounds from bromo- carbonyl compounds and silyl enol ethers

Scheme 5. Synthesis of tetra-substituted furan by coupling 2- bromo-1,3-dicarbonyl compound with silyl enol ethers in one pot

Scheme 6. Synthesis of α-alkylated ketone involving silyl enol ethers and enamides

Scheme 7. Photocatalytic silyl difluoromethylation of silyl enol ethers

Scheme 8. Synthesis of β-nitroketone compounds by photoredox

Scheme 9. Photocatalytic synthesis of α-trifluoromethyl ketones

Scheme 10. Synthesis of γ-trifluoromethyl α,β-unsaturated carbonyl compounds

Scheme 11. Photocatalytic synthesis of pyrrole derivatives

Scheme 12. Photocatalytic synthesis of α-substituted ketones

Scheme 13. Synthesis of α-substituted ketone by photocatalytic reduction of thiazoline salts

Scheme 14. Photoinduced palladium-catalyzed cyclobutanone oxime ester ring-opening, β-H elimination and addition reaction

Scheme 15. Photocatalytic synthesis of β-ketosulfonamides

Scheme 16. Visible-light-mediated synthesis of α-alkyl ketones

Scheme 17. Photocatalytic synthesis of α-difluoromethyl ketone

Scheme 18. Synthesis of α-sulfonylketones involving silyl enol ethers

Scheme 19. Visible light catalysis enabled alkylation of silyl enol ethers with arylsulfonium salts

Scheme 20. Photoinduced synthesis of β-ketosulfone

Scheme 21. Photoinduced synthesis of sulfonated ring compounds

Scheme 22. Photoinduced synthesis of β-fluoroenone

Scheme 23. Photoinduced synthesis of 3,4-di-dihydropyrrole sulfonate

Scheme 24. Photoinduced synthesis of γ-ketoate

Scheme 25. Photoinduced synthesis of α-functionalized ketones/ esters

Scheme 26. Photocatalytic decarboxylative alkylation of N-(acyloxy)phthalimides with silyl enol ethers

Scheme 27. C—H functionalization of photoactivated aromatic hydrocarbons

Scheme 28. Cu-catalyzed synthesis of β-fluorenone

Scheme 29. Fe-catalyzed synthesis of β,β-dichloroenone and β,β-dibromoenone

Scheme 30. Synthesis of α-substituted carbonyl compounds catalyzed by copper

Scheme 31. Cu-catalyzed trifluoromethylation of silyl enol ethers to α-trifluoromethyl ketone

Scheme 32. Synthesis of α-trifluoromethyl ketone catalyzed by copper complexes

Scheme 33. Vanadium-induced cross-coupling reaction

Scheme 34. Fe-catalyzed synthesis of pyrrole derivatives, 1,6- ketonitrile derivatives and imidazoline derivatives

Scheme 35. Cu-catalyzed synthesis of γ-ketonitrile

Scheme 36. Ag-catalyzed synthesis of 1,4-diketones.

Scheme 37. Synthesis of cyclolide by iron-catalyzed ring expansion reaction

Scheme 38. Synthesis of β,β-dichloro-α,β-unsaturated ketone by silyl enol ethers

Scheme 39. Synthesis of β-ketone sulfone without catalyst

Scheme 40. Synthesis of asymmetric 1,4-diketone without catalyst

Scheme 41. The arylation of enol acetate or silyl enol ethers catalyzed by salicylic acid

Scheme 42. Synthesis of α-sulfonyl ketones by I2/TBHP system

Scheme 43. Electrocatalytic formation of new C—C bonds between β-ketoate and silyl enol ethers

Scheme 44. Electrocatalytic synthesis of α-aryl ketones

Scheme 45. Electrocatalytic synthesis of 3,3-disubstituted hydroxyindole

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