过渡金属催化合成吡咯-2-甲酸酯的研究进展

doi:10.6023/cjoc202006048

摘要/Abstract

吡咯-2-甲酸酯广泛存在于生物活性分子中, 在医药领域具有十分重要的应用, 因此吡咯-2-甲酸酯类化合物的合成研究受到了广泛关注. 过渡金属催化的环加成反应在合成吡咯骨架方面应用广泛, 具有区域选择性专一的优点. 且过渡金属配体导向的C—N键构筑方法具有原子步骤经济性较高、效率高、反应条件温和以及选择性高等优点. 按照过渡金属催化剂分类, 对吡咯-2-甲酸酯的[3+2]、[4+1]与[2+2+1]等成环反应的合成方法进行综述, 介绍了过渡金属催化吡咯-2-甲酸酯化合物的机理及其应用, 并对吡咯-2-甲酸酯的合成进行了展望.

关键词: 吡咯-2-甲酸酯, 过渡金属催化, C—N键构筑

Pyrrole-2-carboxylates exist widely in biologically active molecules and have many important applications in the field of medicine. Therefore, the synthesis of pyrrole-2-carboxylates has received extensive attention. The transition metal- catalyzed cycloaddition reactions are widely used in the synthesis of pyrrole skeletons and have the advantages of regio- selectivity. The formation methods of C—N bonds directed by transition metal ligand have some advantages, such as milder reaction conditions, higher atomic step economy, efficiency and selectivity. The reactions of [3+2], [4+1] and [2+2+1] cycloaddition are reviewed, and the reaction mechanism and application of pyrrole-2-carboxylate compounds are introduced under various transition-metal conditions. The prospects of the synthesis of pyrrole-2-carboxylates are also discussed.

Key words: pyrrole-2-carboxylate, transition metal catalysis, C—N bond formation

引用此文

李辞, 李明瑞, 谢宇星, 于杨, 黄菲. 过渡金属催化合成吡咯-2-甲酸酯的研究进展[J]. 有机化学, 2021, 41(2): 594-610.

Ci Li, Mingrui Li, Yuxing Xie, Yang Yu, Fei Huang. Progress in the Synthesis of Pyrrole-2-carboxylate Catalyzed by Transition Metals[J]. Chinese Journal of Organic Chemistry, 2021, 41(2): 594-610.

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图/表 35

图1. 含有吡咯-2-甲酸酯骨架的生物活性分子

Figure 1. Bioactive molecules containing pyrrole-2-carboxylate

图式1. 以吡咯-2-甲酸酯为底物进行修饰改造

Scheme 1. Modification with pyrrole-2-carboxylate as substrate

图式2. 吡咯经典合成方法

Scheme 2. Classical synthetic method of pyrrole

图式3. 合成吡咯-2-甲酸酯的几种成环反应类型

Scheme 3. Several types of ring-forming reactions for the synthesis of pyrrole-2-carboxylate

图式4. Cu催化的二磺酰基乙烯与α-亚氨基酸酯的1,3-偶极环加成反应

Scheme 4. Cu-catalyzed 1,3-dipolar cycloaddition reaction of bissulfonyl ethylene with α-imino acid ester

图式5. 铜催化的磺酰基烯酮与α-亚氨基酸酯的1,3-偶极环加成反应

Scheme 5. Cu-catalyzed 1,3-dipolar cycloaddition reaction of sulfonyl ketene with α-imino acid ester

图式6. Cu和Mn共催化的氨基酸酯类的氧化环化反应

Scheme 6. Cu-Mn-catalyzed oxidative cyclization of amino acid esters

图式7. Cu催化的胺、炔酯和马来酰亚胺的氧化环化反应

Scheme 7. Cu-catalyzed oxidative cyclization of amines, alkynyl esters and maleimides

图式8. 胺、炔酯和马来酰亚胺氧化偶联可能的机理

Scheme 8. Possible mechanism for oxidative coupling of amines, alkyne esters and maleimides

图式9. Cu催化叠氮化物的1,4-加成反应

Scheme 9. Cu-catalyzed 1,4-addition reaction of azide

图式10. 生成吡咯四甲酸酯反应可能的机理

Scheme 10. Possible mechanism for the formation of pyrrole tetracarboxylate

图式11. Cu催化的异氰化合物与炔烃的[3+2]环加成反应

Scheme 11. Cu-catalyzed [3+2] cycloaddition of isocyanide with alkyne

图式12. Cu催化异氰化合物与炔烃环加成反应可能的机理

Scheme 12. Possible mechanism for Cu-catalyzed cycloaddition reaction of isocyanides and alkynes

图式13. 铜催化卡宾插入、迁移反应合成多取代吡咯

Scheme 13. Copper-catalyzed carbene insertion and ester migration for synthesis of polysubtituted pyrroles

图式14. Cu催化卡宾插入烯胺酮反应的机理实验

Scheme 14. Mechanism experiment for the reaction of Cu-cata- lyzed carbene insertion into enaminone

图式15. Ru催化的利用光氧化还原构建吡咯-2-甲酸酯

Scheme 15. Ru-catalyzed construction of pyrrole-2-carboxylate using photooxidation

图式16. Ru催化构建吡咯-2-甲酸酯可能的机理

Scheme 16. Possible mechanism for Ru-catalyzed construction of pyrrole-2-carboxylate

图式17. Au催化丙炔酯衍生物与异噁唑的环化反应

Scheme 17. Au-catalyzed cyclization of propionate derivatives with isoxazole

图式18. Au催化炔酸酯与异噁唑反应可能的机理

Scheme 18. Possible mechanism for Au-catalyzed reaction of acetylenic acid ester and isoxazole

图式19. Au催化炔基氮丙啶环化

Scheme 19. Au-catalyzed cyclization of alkynylaziridines

图式20. Au催化的肟与乙炔二羧酸酯的环异构化反应

Scheme 20. Au-catalyzed ring isomerization of oxime with acetylene dicarboxylate

图式21. Ag催化的芳构化串联反应

Scheme 21. Ag-catalyzed aromatization tandem reaction

图式22. Ag 催化的α-溴苯磺酰乙烯与α-亚氨基酸酯的1,3偶极环加成反应

Scheme 22. Ag-catalyzed 1,3-dipolar cycloaddition of α-bromobenzenesulfonyl ethylene with α-imino acid ester

图式23. Ag催化炔酯与胺的[2+2+1]环化反应

Scheme 23. Ag-catalyzed [2+2+1] cyclization of alkynyl esters with amines

图式24. Ag催化加成/氧化环化反应机理

Scheme 24. Ag-catalyzed mechanistic for the addition/oxidative cyclization reaction

图式25. 活化的异氰酸酯与丙烯酸酯的环化反应

Scheme 25. Cyclization reaction of activated isocyanate and acrylate

图式26. AgOTf催化的[4+1C]插入反应选择性合成吡咯

Scheme 26. AgOTf-catalyzed [4+1C] insertion reaction for selective synthesis of pyrrole

图式27. Ag催化烯胺酮与重氮酯反应的机理实验

Scheme 27. Mechanism experiment for Ag-catalyzed reaction of enaminone with diazo ester

图式28. Ag催化烯胺酮与重氮酯反应可能的机理

Scheme 28. Possible mechanism for Ag-catalyzed reaction of enaminone with diazo ester

图式29. Rh 催化合成β-氟-吡咯-2-甲酸酯的环化过程

Scheme 29. Rh-catalyzed cyclization of β-fluoro-pyrrole-2-carboxylate

图式30. 金属催化叠氮基丙烯酸酯的分子内环化反应

Scheme 30. Metal-catalyzed intramolecular cyclization of azide acrylate

图式31. Rh催化异氰与羰基化合物环化反应

Scheme 31. Rh-catalyzed cyclization of isonitriles with carbonyl compounds

图式32. Pd催化OBO-酮和硝基芳烃的偶连环化反应

Scheme 32. Pd-catalyzed coupling cyclization of OBO-ketones and nitroaromatics

图式33. Pd催化2-胺基-3-碘代丙烯酸酯和内炔烃环化反应

Scheme 33. Pd-catalyzed cyclization of internal alkynes and 2-amino-3-iodoacrylate derivatives

图式34. Pd催化碘代脱氢氨基酸甲酯的环异构化反应

Scheme 34. Pd-catalyzed cyclic isomerization of methyl iodide dehydrogenated amino acid

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