自由基介导的串联环化反应构建七元含氮/氧杂环化合物

doi:10.6023/cjoc202209032

摘要/Abstract

因为七元杂环骨架特殊的化学结构以及所含杂原子的独特化学性质使得其在天然产物及药物分子中得到广泛应用. 然而, 由于含氮/氧七元杂环骨架独特的热力学、动力学特征以及自身特有的跨环作用力等原因, 使得针对这些结构的合成方法学的开发具有很强的挑战性. 因此, 发展简单、高效构筑七元杂环化合物的方法具有重要意义. 相较于传统的合成方法, 自由基反应可以避免较差的原子经济性和苛刻的反应条件的限制. 综述了近年来利用自由基串联环化反应构建七元含氮/氧杂环化合物的合成策略.

关键词: 自由基, 串联环化反应, 七元含氮杂环, 七元含氧杂环

Owing to the special chemical structure of the seven-membered heterocyclic skeleton and the unique chemical properties of the heteroatoms contained, it is widely used in natural products and drug molecules. However, the development of synthetic methodology for these structures is challenging due to the unique thermodynamic and kinetic characteristics of nitrogen/oxygen-containing seven-membered heterocyclic frameworks, as well as their own unique cross-ring forces. Therefore, it is of great significance to develop simple and efficient methods for the construction of seven-membered heterocyclic compounds. Compared with traditional synthetic methods, radical reactions can avoid the limitations of poor atom economy and harsh reaction conditions. In this review, the recent synthetic strategies for the construction of seven-membered nitrogen/oxygen-containing heterocyclic compounds using radical tandem cyclization reactions are summarized.

Key words: free radical, cyclization, seven-membered nitrogen heterocycles, seven-membered oxygen heterocycles

引用此文

赵晓伟, 夏紫琴, 张曼, 周能能. 自由基介导的串联环化反应构建七元含氮/氧杂环化合物[J]. 有机化学, 2022, 42(12): 3995-4023.

Xiaowei Zhao, Ziqin Xia, Man Zhang, Nengneng Zhou. Radical-Mediated Tandem Cyclization to Construct Seven-Membered Nitrogen/Oxygen Heterocycles[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 3995-4023.

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图/表 47

图1. 含有七元杂环的药物

Figure 1. Drugs containing seven-membered heterocycles

图2. 肟醚合成七元含氮杂环

Figure 2. Synthesis of seven-membered nitrogen heterocycles from oxime ethers

图3. 分子内自由基环化反应合成七元含氮杂环化合物

Figure 3. Intramolecular radical cyclization to synthesize seven- membered nitrogen heterocycles

图4. 过氧化月桂酰促进下合成七元含氮杂环

Figure 4. Synthesis of seven-membered nitrogen-containing heterocycles promoted by lauroyl peroxide

图5. Baylis-Hillman反应合成七元氮杂的双环α-内酰胺

Figure 5. Synthesis of seven-membered aza-bicyclic α-lactams by Baylis-Hillman reaction

图6. [2+2]环加成合成三环结构的α-内酰胺

Figure 6. [2+2] cycloaddition to synthesize tricyclic α-lactams

图7. 扩环合成七元环状烷氧基胺

Figure 7. Synthesis of seven-membered cyclic alkoxyamines by ring expansion

图8. Stork催化氢化锡法合成了七元含氮杂环

Figure 8. Synthesis of seven-membered nitrogen heterocycles by Stork-catalyzed tin hydride method

图9. Bu3SnH介导下合成七元氮杂环

Figure 9. Bu3SnH-induced synthesis of seven-membered nitrogen heterocycles

图10. 有机磷自由基介导的环化反应合成七元内酰胺

Figure 10. Organophosphorus radical-mediated cyclisations to afford seven-membered lactams

图11. 双环α-内酰胺和三环α-内酰胺的合成

Figure 11. Synthesis of bicyclic α-lactam and tricyclic α-lactam

图12. 可见光催化合成七元含氮杂环化合物

Figure 12. Visible light-induced synthesis of seven-membered nitrogen heterocycles

图13. 过氧化月桂酰氧化下合成七元含氮杂环

Figure 13. Lauroyl peroxide on pyrimidine and aza seven- membered ring

图14. 2-(2-碘苯基)-N-苯基乙酰胺合成二苯并氮杂酮化合物

Figure 14. Synthesis of dibenzoazepines from 2-(2-iodophenyl)- N-phenylacetamide

图15. 铜催化合成磺酰化苯并氮杂?化合物

Figure 15. Copper-catalyzed synthesis of sulfonated benzoseven-membered nitrogen heterocycle

图16. 通过巴顿酯中间体合成七元含氮杂环

Figure 16. Synthesis of seven-membered nitrogen heterocycles via barton ester intermediates

图17. 铁或铜催化合成含三氟甲基的四环苯并氮杂?衍生物

Figure 17. Iron or copper catalyzed the synthesis of trifluoromethyl-containing tetracyclic benzazepines

图18. 银催化合成磷酸吲哚并氮杂酮衍生物

Figure 18. Silver-catalyzed the synthesis of phosphate indoloazepine derivatives

图19. 铜催化合成二氟甲基化吲哚并氮杂酮衍生物

Figure 19. Copper-catalyzed synthesis of difluoromethylated indoloazepines

图20. 银催化合成苯并氮杂?化合物

Figure 20. Silver-catalyzed synthesis of 2H-benzo[b]azepin-2-ones

图21. 可见光光催化合成苯并氮杂?衍生物

Figure 21. Visible light-induced synthesis of benzazepines

图22. 电催化合成二氟甲基化二苯并氮杂?化合物

Figure 22. Electrochemical synthesis of difluoromethyl-containing dibenzoazepines

图23. 可见光氧化还原合成氟化二苯并[b,e]氮杂?化合物

Figure 23. Visible light-induced synthesis of fluorinated dibenzo[b,e]azepines

图24. 光催化环化合成七元多环内酰胺和内酯

Figure 24. Visible-light-induced synthesis of seven-membered polycyclic lactams and lactones

图25. 铜催化合成七元含氮杂环化合物

Figure 25. Copper-catalyzed synthesis of seven-membered nitrogen heterocycles

图26. 钴催化合成环状胍化合物

Figure 26. Cobalt-catalyzed synthesis of cyclic guanidines

图27. 可见光光氧化还原催化合成磺化二苯并氮杂?化合物

Figure 27. Visible-light photoredox catalytic synthesis of sulfonated dibenzoazepines

图28. 铜催化合成含CF3的二苯并硫氮杂?类化合物

Figure 28. Copper-catalyzed synthesize of CF3-containing dioxodibenzothiazepines

图29. 光氧化还原催化获得二氟烷基化二苯并七元氮杂环

Figure 29. Photoredox-catalyzed acquisition of difluoroalkylated dibenzoseven-membered azacyclics

图30. AgSCF3催化合成含SCF3的二苯并氮杂?或二氧二苯并硫氮杂?类化合物

Figure 30. AgSCF3-catalyzed synthesis of SCF3-substituted dibenzazepines or dioxydibenzothiazepines

图31. 可见光催化合成含SCN的二苯并氮杂?或二氧二苯并硫氮杂?化合物

Figure 31. Visible light-induced synthesis of SCN-containing dibenzodiazepine or dioxodibenzothiazepine

图32. 可见光催化合成二氟酰胺磺酰化二苯并硫氮杂?类化合物

Figure 32. Visible light-induced synthesis of difluoroamide sulfonyl dioxodibenzothiazines

图33. 铜催化合成三氟甲基硫醇化二苯并硫氮杂?类化合物

Figure 33. Cu-catalyzed synthesize of trifluoromethylthiolated dioxodibenzothiazepines

图34. 铜催化合成苯并硫氮杂?化合物

Figure 34. Copper-catalyzed synthesis of benzo[f][1,2]thiazepine 1,1-dioxide

图35. NO2自由基引发的7-endo环化

Figure 35. 7-endo Cyclization triggered by NO2 radicals

图36. 光诱导氮中心自由基的7-endo-trig环化合成七元氮杂环

Figure 36. Light-induced 7-endo-trig cyclization of N-centered radicals to synthesize seven-membered azacyclics

图37. 硒化物合成2,7-二取代的环氧己烷-3-酮

Figure 37. Synthesis of 2,7-disubstituted epoxyhexane-3-ones from selenides

图38. 自由基串联环化反应合成七元氧杂环

Figure 38. Synthesis of oxacycles by tandem radical addition- cyclization reactions

图39. 锰催化合成9-二苯并[b,f]氧杂环庚烷羧酸脂

Figure 39. Manganese catalyzed synthesis of 9-dibenzo[b,f]oxepane carboxylates

图40. 硫酚诱导邻位乙烯基-2-丙炔基醚7-endo环化合成苯并氧杂环庚烷衍生物

Figure 40. Thiophenol-induced 7-endo cyclization of ortho-vinyl-2-propynyl ethers to synthesize oxepane derivatives

图41. 铜催化烯醇化物和亚磺酸钠合成硫醇化七元环醚

Figure 41. Copper-catalyzed synthesis of sulfinated seven-membered cyclic ethers

图42. 可见光氧化还原合成含有CF2的苯并氧杂环庚烷衍生物

Figure 42. Visible light photoredox synthesis of CF2-containing benzoxepane derivatives

图43. 可见光诱导合成磺酰化苯并氧杂环庚二烯类化合物

Figure 43. Visible light-induced synthesis of sulfonated phenoxyzepines

图44. 叔丁基过氧化氢引发自由基环化合成磺酰化苯并氧杂环庚二烯类化合物

Figure 44. tert-Butyl hydroperoxide induced synthesis of sulfonated benzoxazepines

图45. 光氧化还原反应或金属催化反应合成氰基烷基磺酰化苯并氧杂环庚二烯类化合物

Figure 45. Photoredox or metal-catalyzed synthesis of cyanoalkylsulfonylated benzozepines

图46. 自由基环化/磺化反应合成磺化苯并[b]氧杂萜酮衍生物

Figure 46. Synthesis of sulfonated benzo[b]oxeterpenicone derivatives by radical cyclization/sulfonation reaction

图47. 可见光催化合成双-二氟烷基化苯并氧杂环庚二烯类化合物

Figure 47. Visible light-induced synthesis of bis-difluoroalkylated benoxepines

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