碳酸亚乙烯酯: 有机合成化学中的多功能合成子

doi:10.6023/cjoc202401036

摘要/Abstract

近年来, 碳酸亚乙烯酯已成为一种新型、理想的多功能合成子, 广泛应用于丰富多样的有机合成转化中, 特别是在过渡金属催化的C—H官能化领域, 可用于构建含碳、杂环骨架的目标分子. 自2009年Nishii和Miura首次报道了碳酸亚乙烯酯作为“乙炔醇替代物”参与偶联反应以来, 其作为“乙炔替代物”、“C1合成子”、“酰甲基化试剂”及其它功能试剂的应用被陆续报道. 这些进展不仅凸现了碳酸亚乙烯酯的多功能转化性, 也为复杂化合物的合成提供新思路. 根据碳酸亚乙烯酯在合成化学中的不同反应角色, 概述了近年来碳酸亚乙烯酯的最新研究进展, 并对其未来发展提出展望.

关键词: 碳酸亚乙烯酯, C—H官能化, 环化反应, 氮杂环

In recent years, vinylene carbonate has become a new and ideal multifunctional synthon, which is widely used in a variety of organic transformations. Especially in the field of transition metal-catalyzed C—H functionalization, it can be used to construct target molecules containing carbon and heterocyclic skeletons. Since Nishii and Miura first reported that vinylene carbonate participates in coupling reactions as an “ethynol surrogate” in 2009, it has been successively reported as an “acetylene surrogate”, “C1 synthon”, “acylmethylation reagent”, and others. These developments not only highlight the multifunctional transformation of vinylene carbonate, but also provide new ideas for the synthesis of complex compounds. The latest research progress of vinylene carbonate in recent years is summarized and the prospects for its future development based on the different reaction roles of vinylene carbonate in synthetic chemistry are proposed.

Key words: vinyl carbonate, C—H functionalization, cyclization, N-heterocycles

引用此文

林雨, 付海峰, 曹华, 刘想. 碳酸亚乙烯酯: 有机合成化学中的多功能合成子[J]. 有机化学, 2024, 44(7): 2147-2173.

Yu Lin, Haifeng Fu, Hua Cao, Xiang Liu. Vinylene Carbonate: A Versatile Synthon in Organic Synthetic Chemistry[J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2147-2173.

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图/表 39

图式1. 碳酸亚乙烯酯作为多功能合成子在有机合成中的应用

Scheme 1. Application of vinylene carbonate as multifunctional synthon in organic synthesis

图式2. 碳酸亚乙烯酯作为“乙炔醇替代物”的首次报道

Scheme 2. First report on ethylene carbonate as a "ethynol surrogate"

图式3. Rh催化偶氮苯与碳酸亚乙烯酯的[4+1]/[4+2]环化反应

Scheme 3. Rh-catalyzed [4+1]/[4+2] cyclization of azobenzenes and vinylene carbonate

图式4. Rh催化亚磺酰基苯甲酰胺与碳酸亚乙烯酯的环化反应

Scheme 4. Rh-catalyzed cyclization reaction of sulfonylbenzamide with vinyl carbonate

图式5. 钌催化2-芳基喹唑啉酮与碳酸亚乙烯酯的环化反应

Scheme 5. Ru-catalyzed cyclization of 2-arylquinazolinone and ethylene carbonate

图式6. N-芳基二氮杂萘酮/N-芳基吲唑酮与碳酸亚乙烯酯的环化反应

Scheme 6. Annulation reaction of N-arylphthalazinones/N-arylindazolones with vinylene carbonate

图式7. N-芳基二氮杂萘酮与碳酸亚乙烯酯的环化反应机理

Scheme 7. Reaction mechanism of annulation reaction of N-arylphthalazinones with vinylene carbonate

图式8. Rh催化硫叶立德/与碳酸亚乙烯酯的C—H活化/环化反应

Scheme 8. Rhodium-catalyzed C—H activation/annulation of sulfoxonium ylides with vinylene carbonate

图式9. N-氨基吡啶盐与碳酸亚乙烯酯的环化反应

Scheme 9. Cyclization reaction of azinium-N-imines with vinyl carbonate

图式10. 底物范围

Scheme 10. Substrate scope

图式11. 反应机理与产物衍生

Scheme 11. Reaction mechanism and products derivations

图式12. Rh(III)催化碳酸亚乙烯酯作为“乙炔替代物”的C—H/N—H环化反应

Scheme 12. Rhodium-catalyzed C—H/N—H annulation using vinylene carbonate as an oxidizing acetylene surrogate

图式13. Rh(III)催化C—H/N—H环化反应机理

Scheme 13. Mechanism of rhodium-catalyzed C—H/N—H annulation

图式14. 铑催化合成异香豆素

Scheme 14. Synthesis of isocoumarins via Rh-catalysis

图式15. 铑催化咪唑并吡啶和吡唑的氧化C—H/C—H环化反应

Scheme 15. Rhodium-catalyzed oxidative C—H/C—H annulation of imidazopyridines and pyrazole

图式16. 铑催化N-芳基甲亚胺与碳酸亚乙烯酯之间的[4+2]环化

Scheme 16. Rhodium-catalyzed [4+2] annulation between N-arylmethanimines with vinylene carbonate

图式17. 可能的反应机理

Scheme 17. Possible reaction mechanism

图式18. 多环异喹啉[1,2-b]喹唑啉类衍生物的合成

Scheme 18. Synthesis of isoquinolino[1,2-b] quinazolinones

图式19. Rh催化苯甲脒类和碳酸亚乙烯酯的[4+2]环化反应

Scheme 19. Rh-catalyzed annulation of benzamidines with vinylene carbonate

图式20. 铑催化烯胺酮与碳酸亚乙烯酯的C—H键活化及烯基转移反应

Scheme 20. Rhodium-catalyzed C—H bond activation and vinylene transfer of enaminones with vinylene carbonate

图式21. 偶氮苯与碳酸亚乙烯酯的环化反应

Scheme 21. Cyclization of azobenzenes and vinylene carbonate

图式22. Rh(III)催化1-苯基吡唑烷酮与碳酸亚乙烯酯环化反应

Scheme 22. Rh(III)-catalyzed annulation of 1-phenylpyrazolidinones with vinylene carbonate

图式23. Rh催化硫叶立德/N-氨基甲酰基吲哚与碳酸亚乙烯酯的C—H官能化/乙烯基环化反应

Scheme 23. Rhodium-catalyzed direct vinylene annulation of sulfoxonium ylides and N-carbamoylindoles with vinylene carbonate

图式24. Co(III)催化苯甲酰胺或丙烯酰胺与碳酸亚乙烯酯环化反应

Scheme 24. Co(III)-catalyzed annulation of benzamides and acrylamides with vinylene carbonate

图式25. 芳香酰胺与碳酸亚乙烯酯的环化反应

Scheme 25. Cyclization of N-phenylpivalamides with vinylene carbonate

图式26. 锰(II)催化芳香脒与碳酸亚乙烯酯的[4+2]环化反应

Scheme 26. Mn(II)-catalyzed [4+2] annulation of N-arylbenzamidines with vinylene carbonate

图式27. N-异喹啉盐与碳酸亚乙烯酯的1,3-偶极环加成反应合成苯并稠合中氮茚衍生物

Scheme 27. Synthesis of benzo-fused indolizines via the 1,3-dipolar cycloadditions of N-isoquinoline salts with vinylene carbonate

图式28. 脒和碳酸亚乙烯酯的[4+1]环化反应

Scheme 28. [4+1] annulation of amidine with vinylene carbonate

图式29. Rh催化苯胺与碳酸亚乙烯酯的环化反应

Scheme 29. Rh-catalyzed annulation of aniline with vinylene carbonate

图式30. Rh催化芳基偶氮苯与碳酸亚乙烯酯的[4+1]环化反应

Scheme 30. Rh-catalyzed [4+1] cyclization reaction of aryl azobenzene and vinylene carbonate

图式31. 铑催化2-吡咯基/吲哚基苯胺与碳酸亚乙烯酯的形式上[5+1]环化反应

Scheme 31. RhIII-catalyzed formal [5+1] cyclization of 2-pyrrolyl/indolylanilines with vinylene carbonate

图式32. Rh催化酰甲基化反应

Scheme 32. Rh-catalyzed formylmethylation

图式33. Rh催化吲哚衍生物与碳酸亚乙烯酯的C2/C7烷基化反应

Scheme 33. Rh-catalyzed C2/C7 alkylation of indole derivatives with vinyl carbonate

图式34. N-(2-嘧啶基)吲哚的C—H酰甲基化反应

Scheme 34. C—H acetylation of N-(2-pyrimidyl)indoles

图式35. 异噁唑与碳酸亚乙烯酯的酰甲基化反应

Scheme 35. Formylmethylation of isoxazoles with vinylene carbonates

图式36. 钌催化的吲哚啉C—H甲酰甲基化反应

Scheme 36. Ruthenium-catalyzed C—H formylmethylation of indolines

图式37. 铱催化碳酸亚乙烯酯与芳基硼酸的芳基化反应

Scheme 37. Iridium-catalyzed arylation of vinylene carbonate with arylboronic acids

图式38. 2-吲哚苯胺/2-吡咯烷基苯胺与碳酸亚乙烯酯的环化反应

Scheme 38. Annulation of 2-indolylanilines/2-pyrrolylanilines with vinylene carbonate

图式39. 2-吲哚苯胺与碳酸亚乙烯酯的可能反应机理

Scheme 39. Possible reaction mechanism of 2-pyrrolylanilines with vinylene carbonate

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