金催化炔烃分子内环化反应及应用研究进展

doi:10.6023/cjoc202407034

摘要/Abstract

金催化剂由于具有高反应性、独特选择性、对π键的高亲和力等优点, 通常用于活化炔烃、烯烃和联烯等化合物. 其中, 金催化剂不仅能够活化炔烃形成乙烯基金中间体或者金卡宾中间体参与反应, 而且也能够催化炔烃发生分子内环化构建新型杂环或多环化合物. 此综述总结了近八年来金催化炔烃的分子内环化反应, 包括不同亲核性的碳原子和杂原子与炔烃的分子内环化反应, 及其在天然产物全合成领域方面的应用.

关键词: 金催化, 炔烃, 分子内环化反应, 杂环化合物, 反应选择性

As gold catalysts have the advantages of high reactivity, unique selectivity, and high affinity for π bonds, they are usually used to activate alkynes, alkenes, and allenes. Gold catalysts not only promote the activation of alkynes to form vinyl gold intermediates or gold carbene intermediates to participate in the reaction, but also catalyze the intramolecular cyclization to form new types of heterocycles or polycyclic compounds. This review summarizes the gold-catalyzed intramolecular cyclization of alkynes in recent eight years, including the intramolecular cyclization of different nucleophilic carbon-atom and heteroatoms, and its applications in the total synthesis of natural products.

Key words: gold catalysis, alkynes, intramolecular cyclization, heterocyclic compounds, reaction selectivity

引用此文

张旭, 邹佩森, 刘小清, 闭红艳, 莫冬亮. 金催化炔烃分子内环化反应及应用研究进展[J]. 有机化学, 2025, 45(10): 3755-3776.

Xu Zhang, Peisen Zou, Xiaoqing Liu, Hongyan Bi, Dongliang Mo. Recent Progress in Gold-Catalyzed Intramolecular Cyclization of Alkynes and Its Applications[J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3755-3776.

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图/表 48

图1. 金催化炔烃分子内环化反应

Figure 1. Gold-catalyzed intramolecular cyclization of alkynes

图式1. 金催化萘酚化合物分子内去芳构化反应

Scheme 1. Gold-catalyzed intramolecular dearomatization of naphthols

图式2. 金催化1,6-二炔基二硫缩醛的环化反应

Scheme 2. Gold-catalyzed cyclization of 1,6-diynyl dithioacetals

图式3. 金催化亚甲基环丙烷的分子内氢芳基化反应

Scheme 3. Gold(I)-catalyzed intramolecular hydroarylation of methylenecyclopropanes

图式4. 金催化环化合成苯并[a]芴衍生物

Scheme 4. Gold-catalyzed cyclization to synthesize benzo[a]fluorene derivatives

图式5. 金催化分子内环化合成1,2-二氢[c][2,7]萘啶衍生物

Scheme 5. Gold-catalyzed intramolecular cyclization to synthesize 1,2-dihydro[c][2,7]naphthyridine derivatives

图式6. 金催化1,5-二炔的环化反应

Scheme 6. Gold-catalyzed cyclization of 1,5-diynes

图式7. 金催化环化合成茚并[1,2-c]吡咯衍生物

Scheme 7. Gold-catalyzed cyclization to synthesize indeno[1,2-c] pyrroles

图式8. 金催化环化合成氮杂芳香化合物

Scheme 8. Gold-catalyzed cyclization to synthesize aza-aromatic compounds

图式9. 金催化环化合成苯并[c,d]吲哚衍生物

Scheme 9. Gold-catalyzed cyclization to synthesize benzo[c,d]indole derivatives

图式10. 金催化联烯基炔的双环化反应

Scheme 10. Gold(I)-catalyzed bis-cyclization of allenynes

图式11. 金催化内炔的碳酰基化反应

Scheme 11. Gold-catalyzed carboxyalkylation of internal alkynes

图式12. 金催化分子内氢烷基化合成茚

Scheme 12. Gold-catalyzed intramolecular hydroalkylation to synthesize indenes

图式13. 金催化炔基吲哚酮选择性环化构建咔唑类化合物

Scheme 13. Gold-catalyzed selective synthesis of indolyl-ynones to prepare carbazoles

图式14. 金催化N-炔丙基色胺衍生物区域选择性环化合成螺吲哚啉

Scheme 14. Gold(I)-catalyzed regioselective cyclizations of N-propargyl tryptamines to synthesize spiroindoleni

图式15. 金催化炔基吲哚选择性环化构建吴茱萸次碱类似物

Scheme 15. Gold-catalyzed selective cyclization of alkynyl-tethered indoles to prepare rutaecarpine derivatives

图式16. 金催化吲哚分子内去芳构化反应

Scheme 16. Gold-catalyzed intramolecular dearomatization reactions of indoles

图式17. 金催化N-炔丙基吲哚衍生物的去芳构化螺环化反应

Scheme 17. Gold-catalyzed dearomatization spirocyclization reactions of N-propargyl tryptamines

图式18. 金(I)催化选择性环化制备吴茱萸次碱衍生物

Scheme 18. Gold(I)-catalyzed selective cyclization to prepare pseudorutaecarpine derivatives

图式19. 金(I)催化1,6-二炔吲哚化合物的去芳构化/环化反应

Scheme 19. Gold(I)-catalyzed dearomatization/cyclization of 1,6-diyne

图式20. 金(I)催化1,6-二炔吲哚化合物去芳构化的反应机理

Scheme 20. Possible mechanism of gold(I)-catalyzed dearomatization of 1,6-diyne compounds

图式21. 金(I)催化炔基螺环氧吲哚环异构化/扩环反应

Scheme 21. Gold-catalyzed cycloisomerization/ring expansion of alkynyl spiro-epoxyoxindoles

图式22. 金(I)催化烷基炔基吲哚分子内氢芳基化反应

Scheme 22. Gold(I)-catalyzed intramolecular hydroarylation of alkynylindoles

图式23. 金(I)催化一锅法构建手性二氢咔唑

Scheme 23. Gold(III)/Yb(III)-catalyzed synthesis of chiral dihydrocarbazoles in one pot reaction

图式24. 金催化呋喃炔选择性环化反应

Scheme 24. Gold-catalyzed selective cyclization of furanyl-alkynes

图式25. 金(III)催化N-炔基-2-吡咯喹唑啉酮选择性环化反应

Scheme 25. Gold (III)-catalyzed selective cyclization of alkynyl quinazolinone-tethered pyrroles

图式26. 金催化环化合成茚酮衍生物

Scheme 26. Gold-catalyzed cyclization to synthesize indenone derivatives

图式27. 金催化下炔酰胺碳烷氧基化反应

Scheme 27. Gold-catalyzed carboalkoxylation of ynamides

图式28. 金催化呋喃-炔酮的螺环化反应

Scheme 28. Gold-catalyzed spirocyclization of furan-ynones

图式29. 金催化呋喃-炔酮的氢芳基化反应

Scheme 29. Gold-catalyzed asymmetric hydroarylation of furan-ynones

图式30. 金(I)催化选择性合成1,1'-联萘-2,3'-二酚

Scheme 30. Gold(I)-catalyzed atroposelective synthesis of 1,1'-binaphthalene-2,3'-diols

图式31. 金(I)催化邻炔芳基二茂铁衍生物不对称氢芳基化反应

Scheme 31. Gold(I)-catalyzed asymmetric hydroarylation of ortho-alkynylaryl ferrocenes derivatives

图式32. 金催化1-(2′-叠氮基芳基)丙炔醇的环化反应

Scheme 32. Gold-catalyzed cyclization of 1-(2′-azidoaryl) propynols

图式33. 金催化的氢胺化反应

Scheme 33. Gold-catalyzed of hydroaminations

图式34. 金催化区域选择性合成吡唑并[1,4]噁唑啉

Scheme 34. Gold-catalyzed regioselective synthesis of pyrazolo[1,4]oxazepines

图式35. 金催化不对称合成3-吡咯啉化合物

Scheme 35. Gold-catalyzed asymmetric to synthesize 3-pyrroline compounds

图式36. 金催化二芳基硫肟亚胺的环化反应

Scheme 36. Gold-catalyzed cyclization of diarylthiooximines

图式37. 金催化炔二醇的环化反应

Scheme 37. Gold-catalyzed cyclization of alkynediols

图式38. 金催化重排/环化合成2,5-二氢呋喃

Scheme 38. Gold-catalyzed rearrangement/cyclization to synthesize 2,5-dihydrofurans

图式39. 金/铱催化炔酰胺环化/不对称烯丙基串联反应

Scheme 39. Gold/Iridium catalyzed alkynylamide cyclization/asymmetric allylic alkylation cascade reaction

图式40. 金催化环化反应在citreoviranol (1)合成中的应用

Scheme 40. Application of gold-catalyzed cyclization in the total synthesis of citreoviranol (1)

图式41. 金催化环化反应在(±)-Strictamine合成中的应用

Scheme 41. Application of gold-catalyzed cyclization in the total synthesis of (±)-Strictamine

图式42. 金催化反应在三环吲哚合成中的应用

Scheme 42. The application of gold-catalyzed cyclization in the synthesis of tricyclic indolines

图式43. 金催化环化反应在orientalol F合成中的应用

Scheme 43. Application of gold-catalyzed cyclization in the total synthesis of orientalol F

图式44. 金催化环化反应在(＋)-Strictamine合成中的应用

Scheme 44. Application of gold-catalyzed cyclization in the total synthesis of (＋)-strictamine

图式45. 金催化环化反应在()-aspidophylline A合成中的应用

Scheme 45. Application of gold-catalyzed cyclization in the total synthesis of ()-aspidophylline A

图式46. 金催化环化反应在Vindorosine合成中的应用

Scheme 46. Application of gold-catalyzed cyclization in the total synthesis of Vindorosine

图式47. 金催化环化反应在脱氧糖合成中的应用

Scheme 47. Application of gold-catalyzed cyclization in the synthesis of dideoxy sugar

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