氮杂环卡宾催化醛类化合物的极性反转

doi:10.6023/cjoc202401009

摘要/Abstract

醛类化合物是一类重要的有机化合物, 广泛用于有机合成中. 其典型反应是作为亲电试剂与各种亲核试剂发生加成反应. 羰基的亲电性限制了醛类化合物在合成中的进一步应用和发展. 自从化学家发现氰根离子能够改变苯甲醛的反应极性, 极性反转的策略备受关注. 氮杂环卡宾是一类重要的有机小分子催化剂, 在有机催化领域扮演着重要的角色. 在氮杂环卡宾催化醛类化合物的极性反转方面研究, 取得了一系列重要研究进展. 系统介绍了氮杂环卡宾催化醛类化合物的极性反转, 总结了极性反转碳原子的位置以及极性反转后发生的反应, 旨在引起化学工作者对该领域有更多的关注, 发展氮杂环卡宾催化的新模式、新反应.

关键词: 氮杂环卡宾, 有机催化, 醛, 极性反转

Aldehyde compounds are a class of important organic compounds, which are widely used in organic synthesis. The typical reaction of aldehydes is the addition reaction with various nucleophiles as electrophiles. However, the electrophilicity of aldehyde carbonyl group limits the further application and development of aldehydes in synthesis. Since chemists discovered that cyanogen ions can change the reaction polarity of benzaldehyde, the strategy of umpolung has attracted much attention. N-Heterocyclic carbene (NHC) is a kind of important small organic molecule catalyst, which plays a key role in the field of organic catalysis. A series of important advances have been made in the study of the umpolung of aldehyde compounds catalyzed by NHC. The umpolung of aldehydes catalyzed by NHCs is introduced, and the positions of carbon atoms and the reactions of umpolung are summarized with the purpose of attracting much attention to this research field, and the development of new models and reactions within NHC catalysis.

Key words: N-heterocyclic carbene, organocatalysis, aldehyde, umpolung

引用此文

赵明, 颜瑞, 陈虎. 氮杂环卡宾催化醛类化合物的极性反转[J]. 有机化学, 2024, 44(7): 2204-2215.

Ming Zhao, Rui Yan, Hu Chen. N-Heterocyclic Carbene Catalyzed the Umpolung of Aldehyde Compounds[J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2204-2215.

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图/表 37

图式1. 氮杂环卡宾作用下醛的极性反转

Scheme 1. Aldehyde umpolung enabled by N-heterocyclic carbenes

图式2. Breslow中间体

Scheme 2. Breslow intermediate

图式3. Breslow中间体发生的各类反应

Scheme 3. Various reactions occurring in Breslow intermediate

图式4. 交叉安息香缩合反应和机理

Scheme 4. Cross-benzoin reaction and its mechanism

图式5. 氮杂环卡宾催化分子内交叉安息香缩合反应

Scheme 5. NHC-catalyzed intramolecular cross-benzoin reaction

图式6. 糖类化合物和不饱和酮的分子间Stetter反应

Scheme 6. Intermolecular Stetter reactions of carbohydrates with enones

图式7. 氮杂环卡宾催化的分子内Stetter反应去对称化

Scheme 7. Desymmetrization through NHC-catalyzed intramolecular Stetter reaction

图式8. 氮杂环卡宾催化未活化双键的氢酰化反应

Scheme 8. NHC-catalyzed hydroacylation of unactivated double bonds

图式9. 氮杂环卡宾催化环丙烯的氢酰化反应

Scheme 9. NHC-catalyzed hydroacylation of cyclopropenes

图式10. 氮杂环卡宾催化醛和烯胺之间的交叉偶联反应

Scheme 10. NHC-catalyzed cross-couplings of aldehydes and olefins

图式11. 氮杂环卡宾催化未活化炔烃的氢酰化反应

Scheme 11. NHC-catalyzed hydroacylation of unactivated alkynes

图式12. 氮杂环卡宾催化的氢酰化/Stetter串联反应

Scheme 12. NHC-catalyzed hydroacylation-Stetter reaction cascade

图式13. 氮杂环卡宾催化的SN1取代反应

Scheme 13. NHC-catalyzed SN1-substitution reaction

图式14. 氮杂环卡宾催化的分子间SN2取代反应

Scheme 14. NHC-catalyzed intermolecular SN2-substitution reaction

图式15. 氮杂环卡宾催化的分子内SN2'取代反应

Scheme 15. NHC-catalyzed intramolecular SN2'-substitution reaction

图式16. 氮杂环卡宾催化的不对称分子内亲核取代反应

Scheme 16. NHC-catalyzed enantioselective intramolecular nucleophilic substitution reaction

图式17. 氮杂环卡宾催化醛与非活化卤化物的交叉偶联

Scheme 17. NHC-catalyzed cross-coupling of unactivated halides and aldehydes

图式18. Azolium enolate中间体

Scheme 18. Azolium enolate intermediate

图式19. 氮杂环卡宾催化吡咯吲哚酮的合成

Scheme 19. NHC-catalyzed synthesis of pyrroloindolones

图式20. 氮杂环卡宾催化三氟甲基二氢吡喃酮的合成

Scheme 20. NHC-catalyzed synthesis of trifluoromethyl dihydropyranones.

图式21. 氮杂环卡宾催化α-氯代醛与吡唑啉酮的[4+2]环加成反应

Scheme 21. NHC-catalyzed [4+2] cycloaddition of α-chloro- aldehydes with pyrazolones

图式22. 氮杂环卡宾催化螺环内酰胺的合成

Scheme 22. NHC-catalyzed synthesis of spirocyclic oxindolo-β-lactams

图式23. 氮杂环卡宾催化的不对称[2+2+2]环加成反应

Scheme 23. NHC-catalyzed [2+2+2] enantioselective cycloaddition

图式24. 氮杂环卡宾催化的[2+2]和[2+2+2]环加成反应

Scheme 24. NHC-catalyzed [2+2] and [2+2+2] cycloaddition

图式25. 氮杂环卡宾催化的不对称[8+2]环加成反应

Scheme 25. NHC-catalyzed [8+2] enantioselective cycloaddition

图式26. Homoenolate中间体

Scheme 26. Homoenolate intermediate

图式27. 氮杂环卡宾催化[3+2]环加成合成螺杂环化合物

Scheme 27. Synthesis of spiro-heterocycles by NHC-catalyzed [3+2] cycloaddition

图式28. 氮杂环卡宾催化哒嗪酮的合成

Scheme 28. NHC-catalyzed synthesis of pyridazinones

图式29. 氮杂环卡宾催化苯并ε内酯的合成

Scheme 29. NHC-catalyzed synthesis of benzo-ε-lactones

图式30. 氮杂环卡宾催化的不对称[4+3]环加成反应

Scheme 30. Asymmetric [4+3] cycloaddition reaction catalyzed by NHC

图式31. 氮杂环卡宾催化的不饱和醛与硝基烯的加成

Scheme 31. NHC-catalyzed addition of enals and nitroalkenes

图式32. 不饱和醛的不对称β质子化

Scheme 32. Enantioselective β protonation of enals

图式33. Azolium dienolate中间体

Scheme 33. Azolium dienolate intermediate

图式34. 氮杂环卡宾催化的不饱和醛与偶氮二羧酸酯的环化

Scheme 34. NHC-catalyzed [4+2] annulation of enals and azodicarboxylates

图式35. 氮杂环卡宾催化[4+3]环加成合成七元杂环化合物

Scheme 35. Synthesis of seven-membered heterocyclic compounds by NHC-catalyzed [4+3] cycloaddition

图式36. Azolium trienolate中间体

Scheme 36. Azolium trienolate intermediate

图式37. 氮杂环卡宾催化的对映选择性Mannich反应

Scheme 37. NHC-catalyzed enantioselective Mannich reaction

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