有机膦催化合成中环化合物的研究进展

doi:10.6023/cjoc202405021

摘要/Abstract

中环(7~11元环)是一类重要的有机分子骨架, 广泛存在于药物、农药以及许多具有生物活性的天然产物中, 在有机合成化学中占有重要地位. 有机小分子催化反应是合成中环化合物的重要方法之一, 其中, 有机膦催化具有成本低廉、环境友好以及催化剂易于回收利用等优点, 为中环化合物的合成提供了一条经济而高效的途径. 因此, 近几十年来, 该研究领域受到了持续而广泛的关注. 本综述将对有机膦催化合成中环化合物的研究进展进行总结, 详细阐述不同反应底物类型、反应机理等.

关键词: 有机催化, 膦催化剂, 环化反应, 中环化合物

Medium-sized rings (7~11 membered ring) are a class of important skeleton in organic molecules, which are commonly found in drugs, pesticides and many biologically active natural products, and play essential roles in organic synthetic chemistry. Organo-catalysis is an important methodology for the synthesis of medium-sized ring compounds, among which, organophosphine catalysis has the advantages of low cost, environmental friendliness, and easy recycling, which provides an economical and efficient route for the synthesis of medium-sized ring compounds. Therefore, this field of research has received continuous and extensive attention in recent decades. In this review, the research progress on the organophosphine-catalyzed synthesis of medium-sized ring compounds is summarized, detailing the different types of reaction substrates, reaction mechanisms, etc.

Key words: organocatalysis, phosphine catalysts, annulation reaction, medium-sized ring compounds

引用此文

潘旭玲, 黄有. 有机膦催化合成中环化合物的研究进展[J]. 有机化学, 2024, 44(12): 3609-3620.

Xuling Pan, You Huang. Progress in Synthesis of Medium-Sized Ring Compounds Catalyzed by Organophosphine[J]. Chinese Journal of Organic Chemistry, 2024, 44(12): 3609-3620.

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图/表 38

图式1. PPh3催化无取代联烯酸酯和缺电子烯烃的[3＋2]环化反应

Scheme 1. PPh3-catalyzed [3＋2] annulation reaction of unsubstituted allenoates and electron deficient olefins

图式2. PPh3催化无取代联烯酸酯/联烯酮和环庚三烯酮的 [2＋8]环化反应

Scheme 2. PPh3-catalyzed [2＋8] annulation reaction of unsubstituted allenoates/allenones and tropone

图式3. PPh3催化无取代联烯酸酯和3-色酮甲醛衍生物的[3＋4]环化反应

Scheme 3. PPh3-catalyzed [3＋4] annulation reaction of unsubstituted allenoates and 3-chromanone formaldehyde derivatives

图式4. PPh3催化无取代联烯酸酯与香豆灵酸甲酯的[3＋4]环化反应

Scheme 4. PPh3-catalyzed [3＋4] annulation reaction of unsubstituted allenoates and methyl coumalate

图式5. PBu3催化α-取代联烯酸酯和偶氮甲亚胺的[4＋3]环化反应

Scheme 5. PBu3-catalyzed [3＋4] annulation reaction of α-substituted allenoates and azomethine imines

图式6. PCy3催化无取代联烯酸酯和偶氮甲亚胺的[3＋2＋3]环化反应

Scheme 6. PCy3-catalyzed [3＋2＋3] annulation reaction of unsubstituted allenoates and azomethine imines

图式7. P(NEt2)3催化无取代联烯酸酯和甲亚胺的[3＋2＋3]环化反应

Scheme 7. P(NEt2)3-catalyzed [3＋2＋3] annulation reaction of unsubstituted allenoates and azomethine imines

图式8. P(NEt2)3催化无取代联烯酸酯的环化反应

Scheme 8. P(NEt2)3-catalyzed annulation reaction of unsubstituted allenoates

图式9. PBu3催化α-取代联烯酸酯和C,N-环偶氮亚胺的[4＋3]环化反应

Scheme 9. PBu3-catalyzed [4＋3] annulation reaction of α-substituted allenoates and C,N-cyclic azomethine imines

图式10. PPh3催化γ-甲基取代联烯酸酯和邻羟基苯甲醛衍生的亚胺的连续环化反应

Scheme 10. PPh3-catalyzed sequential annulation reaction of γ-methyl-substituted allenoates and o-hydroxybenzaldehyde- derived imines

图式11. PPh3催化β′-乙酰氧基取代联烯酸酯和2-酰基-3-甲基丙烯腈的[4＋4]环化反应

Scheme 11. PPh3-catalyzed annulation reaction of β′-acetoxy- substituted allenoates and 2-acyl-3-methylacrylonitrile

图式12. PBu3催化α-取代联烯酸酯和C,N-环芳香偶氮亚胺的[4＋3]环化反应

Scheme 12. PBu3-catalyzed [4＋3] annulation reaction of α-substituted allenoates and C,N-cyclic aromatic azomethine imines

图式13. 手性膦催化α-取代联烯酸酯和C,N-环芳香偶氮亚胺的[4＋3]环化反应

Scheme 13. Chiral phosphine-catalyzed [4＋3] annulation reaction of α-substituted allenoates and C,N-cyclic aromatic azomethine imines

图式14. 手性膦催化α-取代联烯酮和α,β-不饱和亚胺的[4＋4]环化反应

Scheme 14. Chiral phosphine-catalyzed [4＋4] annulation reaction of α-substituted allenoates and α,β-unsaturated imines

图式15. P(4-MeOC6H4)3催化无取代联烯酸酯和苯并噻吩衍生的活泼烯烃的连续环化反应

Scheme 15. P(4-MeOC6H4)3-catalyzed sequential annulation reaction of unsubstituted allenoates and thioaurone derivatives

图式16. PMe2Ph催化γ-取代联烯酸酯和环庚三烯衍生物的环化反应

Scheme 16. PMe2Ph-catalyzed annulation reaction of γ-sub- stituted allenoates and heptafulvenes

图式17. PPh3催化β′-乙酰氧基取代联烯酸酯与邻羟基活泼亚胺的[4＋3]环化反应

Scheme 17. PPh3-catalyzed [4＋3] annulation reaction of β′-substituted allenoates and o-hydroxyactive imines

图式18. 手性膦催化γ-取代联烯酸酯和氮杂环庚三烯酮的 [2＋8]环化反应

Scheme 18. Chiral phosphine-catalyzed [2＋8] annulation reaction of γ-substituted allenoates and azaheptafulvenes

图式19. PPh3催化β′-乙酰氧基取代联烯酸酯与1,5-双亲核试剂的[4＋5]环化反应

Scheme 19. PPh3-catalyzed [4＋5] annulation reaction of β′-substituted allenoates and 1,5-dinucleophiles

图式20. P(4-MeOC6H4)3催化α-取代联烯酸酯和色酮-3-甲醛的[6＋1]环化反应

Scheme 20. P(4-MeOC6H4)3-catalyzed [6＋1] annulation reaction of α-substituted allenoates and chromone carboxaldehyde

图式21. P(4-MeOC6H4)3催化β′-乙酰氧基取代联烯酸酯和苯并咪唑衍生的1C,3N-双亲核试剂的[4＋3]环化反应

Scheme 21. P(4-MeOC6H4)3-catalyzed [4＋3] annulation reaction of β′-acetoxy-substituted allenoates and benzimidazole- derived 1C,3N-dinucleophiles

图式22. PPh3催化MBH衍生物与环庚三烯酮的[3＋6]环化反应

Scheme 22. PPh3-catalyzed [3＋6] annulation reaction of MBH derivatives and tropone

图式23. PPh3催化MBH碳酸酯与香豆灵酸甲酯的[3＋4]环化反应

Scheme 23. PPh3-catalyzed [3＋4] annulation reaction of MBH carbonates and methyl coumalate

图式24. P(4-MeC6H4)3催化MBH碳酸酯与1,4-双亲核试剂的[3＋4]环化反应

Scheme 24. P(4-MeC6H4)3-catalyzed [3＋4] annulation reaction of MBH carbonates and 1,4-dinucleophiles

图式25. P(4-MeOC6H4)3催化MBH碳酸酯与氮杂二烯的[3＋4]环化反应

Scheme 25. P(4-MeOC6H4)3-catalyzed [3＋4] annulation reaction of MBH carbonates and N-tosyl azadienes

图式26. 溶剂控制的MBH碳酸酯与苯并噻吩衍生物的[3＋4]环化反应

Scheme 26. Solvent-controlled [3＋4] annulation reaction of MBH carbonates and benzothiophene derivatives

图式27. 膦催化未修饰MBH醇与偶氮亚胺的[3＋4]连续环化反应

Scheme 27. Phosphine-catalyzed sequential annulation reaction of unmodified MBH alcohols and azomethine imines

图式28. 催化剂控制的MBH碳酸酯与氟化酰亚胺酰氯的 [3＋4]环化反应

Scheme 28. Catalysts-controlled [3＋4] annulation reaction of MBH carbonates and fluorinated imidoyl chlorides

图式29. PPh3/Pd(0)协同催化MBH碳酸酯与乙烯基苯并噁嗪酮的[3＋4]环化反应

Scheme 29. PPh3/Pd(0) co-catalyzed [3＋4] annulation reaction of MBH carbonates and vinyl benzoxazinanones

图式30. PPh3催化MBH碳酸酯和二氰基取代环庚三烯衍生物的[3＋6]环化反应

Scheme 30. PPh3-catalyzed [3＋6] annulation reaction of MBH carbonates and dicyanoheptafulvene

图式31. 膦催化MBH碳酸酯与双亲核吲哚衍生物的[3＋4]环化反应

Scheme 31. Phosphine-catalyzed [3＋4] annulation reaction of MBH carbonates and dinucleophilic indole derivatives

图式32. PBu3催化乙烯基环丙烷的开环重排反应

Scheme 32. PBu3-catalyzed ring-opening rearrangement reactions of vinylcyclopropanes

图式33. 手性膦催化二酮的分子内MBH环化反应

Scheme 33. Chiral phosphine-catalyzed intramolecular MBH annulation reaction of ketoenone

图式34. PBu3催化分子内MBH环化反应

Scheme 34. PBu3-catalyzed intramolecular MBH annulation reaction

图式35. PPh3催化炔酸乙酯与1,5-双亲核试剂的[2＋5]环化反应

Scheme 35. PPh3-catalyzed [2＋5] annulation reaction of alkynes and 1,5-dinucleophiles

图式36. PPh3催化乙炔二羧酸酯与氨基磺酸酯衍生的环状亚胺之间的扩环反应

Scheme 36. PPh3-catalyzed ring-expansion reactions of sulfamate-derived cyclic imines and acetylenedicarboxylates

图式37. PPh3催化炔基半缩醛的分子内环化反应

Scheme 37. PPh3-catalyzed intramolecular annulation reaction of alkynyl hemiketals

图式38. PPh2Et催化炔酮与邻氨基苯甲醛的[3＋4]环化反应

Scheme 38. PPh2Et-catalyzed [3＋4] annulation reaction of ynones and 2-sulfonamidobenzaldehyes

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