N-Heterocyclic Carbene Catalyzed the Umpolung of Aldehyde Compounds

doi:10.6023/cjoc202401009

Abstract

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

Cite this article

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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Fig. & Tab. 37

Scheme 1. Aldehyde umpolung enabled by N-heterocyclic carbenes

Scheme 2. Breslow intermediate

Scheme 3. Various reactions occurring in Breslow intermediate

Scheme 4. Cross-benzoin reaction and its mechanism

Scheme 5. NHC-catalyzed intramolecular cross-benzoin reaction

Scheme 6. Intermolecular Stetter reactions of carbohydrates with enones

Scheme 7. Desymmetrization through NHC-catalyzed intramolecular Stetter reaction

Scheme 8. NHC-catalyzed hydroacylation of unactivated double bonds

Scheme 9. NHC-catalyzed hydroacylation of cyclopropenes

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

Scheme 11. NHC-catalyzed hydroacylation of unactivated alkynes

Scheme 12. NHC-catalyzed hydroacylation-Stetter reaction cascade

Scheme 13. NHC-catalyzed SN1-substitution reaction

Scheme 14. NHC-catalyzed intermolecular SN2-substitution reaction

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

Scheme 16. NHC-catalyzed enantioselective intramolecular nucleophilic substitution reaction

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

Scheme 18. Azolium enolate intermediate

Scheme 19. NHC-catalyzed synthesis of pyrroloindolones

Scheme 20. NHC-catalyzed synthesis of trifluoromethyl dihydropyranones.

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

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

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

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

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

Scheme 26. Homoenolate intermediate

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

Scheme 28. NHC-catalyzed synthesis of pyridazinones

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

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

Scheme 31. NHC-catalyzed addition of enals and nitroalkenes

Scheme 32. Enantioselective β protonation of enals

Scheme 33. Azolium dienolate intermediate

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

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

Scheme 36. Azolium trienolate intermediate

Scheme 37. NHC-catalyzed enantioselective Mannich reaction

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