烯醇硅醚参与的自由基反应研究进展

doi:10.6023/cjoc202402007

摘要/Abstract

由于烯醇硅醚具有独特的反应活性, 其在有机合成中得到了广泛的应用. 烯醇硅醚能参与Mukaiyama aldol反应和Mukaiyama-Michael加成反应等经典有机合成反应, 从而构建新的C—C键. 但是由于离子型反应的局限性, 很多复杂分子的合成需要借助更多新型高效的反应, 而烯醇硅醚参与的自由基反应能够在多种反应体系中展现出良好的性能. 总结了近十年来烯醇硅醚作为多功能和高效的反应前体合成α-取代羰基化合物和其他功能有机分子的反应, 并讨论了各种反应体系(光促进、金属催化、无金属参与和电催化)下研究人员对反应的设计、机理的研究以及该研究课题未来的展望.

关键词: 烯醇硅醚, 自由基反应, α-取代羰基化合物, 过渡金属

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

引用此文

张朝阳, 罗维纬, 周俊. 烯醇硅醚参与的自由基反应研究进展[J]. 有机化学, 2024, 44(9): 2658-2681.

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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图/表 46

图1. 具有生物活性的α-取代羰基衍生物

Figure 1. Biologically active α-substitued carbonyl derivatives

图式1. 光催化碘代氟烷烃与烯醇硅醚合成含氟酮

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

图式2. 光催化一锅法合成3-氟吡啶

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

图式3. α-CF2CO2Me取代化合物的合成

Scheme 3. Synthesis of α-CF2CO2Me substituted compounds

图式4. 溴代羰基化合物与烯醇硅醚合成1,4-二羰基化合物

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

图式5. 2-溴-1,3-二羰基化合物与烯醇硅醚偶联一锅法合成四取代呋喃

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

图式6. 烯醇硅醚和烯胺参与合成α-烷基化酮

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

图式7. 光催化烯醇硅醚的硅烷基二氟甲基化反应

Scheme 7. Photocatalytic silyl difluoromethylation of silyl enol ethers

图式8. 光氧化还原合成β-硝基酮化合物

Scheme 8. Synthesis of β-nitroketone compounds by photoredox

图式9. 光催化合成α-三氟甲基酮

Scheme 9. Photocatalytic synthesis of α-trifluoromethyl ketones

图式10. 光催化合成γ-三氟甲基化α,β-不饱和羰基化合物

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

图式11. 光催化合成吡咯啉衍生物

Scheme 11. Photocatalytic synthesis of pyrrole derivatives

图式12. 光催化合成α-取代酮

Scheme 12. Photocatalytic synthesis of α-substituted ketones

图式13. 光催化还原噻唑啉盐合成α-取代酮

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

图式14. 光诱导钯催化环丁酮肟酯开环、β-H消除和加成反应

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

图式15. 光催化合成β-酮磺酰胺

Scheme 15. Photocatalytic synthesis of β-ketosulfonamides

图式16. 可见光介导合成α-烷基酮

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

图式17. 光催化合成α-二氟甲基化酮

Scheme 17. Photocatalytic synthesis of α-difluoromethyl ketone

图式18. 烯醇硅醚参与的合成α-磺酰化酮

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

图式19. 可见光催化烯醇硅醚与芳基锍盐的烷基化反应

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

图式20. 光诱导合成β-酮基砜

Scheme 20. Photoinduced synthesis of β-ketosulfone

图式21. 光诱导合成磺化环状化合物

Scheme 21. Photoinduced synthesis of sulfonated ring compounds

图式22. 光诱导合成β-氟烯酮

Scheme 22. Photoinduced synthesis of β-fluoroenone

图式23. 光诱导合成磺化3,4-双二氢-吡咯

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

图式24. 光诱导合成γ-酮酸酯

Scheme 24. Photoinduced synthesis of γ-ketoate

图式25. 光诱导合成α-官能团化酮/酯

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

图式26. 光诱导烯醇硅醚与N-(酰氧基)邻苯二甲酰亚胺脱羧烷基化反应

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

图式27. 光活化芳烃C—H功能化反应

Scheme 27. C—H functionalization of photoactivated aromatic hydrocarbons

图式28. 铜催化合成β-氟烯酮

Scheme 28. Cu-catalyzed synthesis of β-fluorenone

图式29. 铁催化合成β,β-二氯烯酮和β,β-二溴烯酮

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

图式30. 铜催化合成α-取代羰基化合物

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

图式31. 铜催化烯醇硅醚三氟甲基化合成α-三氟甲基酮

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

图式32. 铜配合物催化合成α-三氟甲基酮

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

图式33. 钒诱导的交叉偶联反应

Scheme 33. Vanadium-induced cross-coupling reaction

图式34. 铁催化合成吡咯衍生物、1,6-酮腈衍生物和咪唑啉衍生物

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

图式35. 铜催化合成γ-酮腈

Scheme 35. Cu-catalyzed synthesis of γ-ketonitrile

图式36. 银催化合成1,4-二酮化合物

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

图式37. 铁催化扩环反应合成环内酯反应

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

图式38. 烯醇硅醚合成β,β-二氯-α,β-不饱和酮

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

图式39. 无催化剂合成β-酮砜

Scheme 39. Synthesis of β-ketone sulfone without catalyst

图式40. 无催化剂合成非对称1,4-二酮

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

图式41. 水杨酸催化烯醇乙酸酯或烯醇硅醚的芳基化反应

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

图式42. I2/TBHP体系合成α-磺酰基酮

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

图式43. 电催化β-酮酸酯与烯醇硅醚生成新C—C键

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

图式44. 电催化合成α-芳基酮

Scheme 44. Electrocatalytic synthesis of α-aryl ketones

图式45. 电催化合成3,3-二取代的羟吲哚

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

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