Kinetic Resolutions Enabled by N-Heterocyclic Carbene Catalysis: An Update

doi:10.6023/cjoc202308023

Abstract

Kinetic resolution is one of the most commonly used methods allowing access to enantioenriched compounds. The last two decades have seen the rapid development of kinetic resolutions enabled by N-heterocyclic carbene catalysis, and part of the achievements have been summarized in our previous review paper published in 2017. Since then, a series of new advances have been realized, and this review will provide an update of this field covering reports from mid-2017 to 2023.

Key words: kinetic resolution, N-heterocyclic carbene, asymmetric catalysis, racemates, enantioenriched compounds

Cite this article

Shuang Yang, Xinqiang Fang. Kinetic Resolutions Enabled by N-Heterocyclic Carbene Catalysis: An Update[J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 448-480.

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Fig. & Tab. 38

Figure 1. Structures, relationships, and reactivities of various NHC intermediates

Scheme 1. Kinetic resolution of trans-γ-lactams

Scheme 2. Site- and enantioselective kinetic resolution of 1,2-diols

Scheme 3. Synthesis of axially chiral anilides via kinetic resolution

Scheme 4. Preparation of optically pure dihydropyranones via divergent strategy

Scheme 5. NHC-catalyzed atroposelective acylation of biphenols

Scheme 6. NHC-catalyzed atroposelective synthesis of axially chiral biaryl amino-alcohols

Scheme 7. NHC-catalyzed kinetic resolution of racemic NOBIN analogs

Scheme 8. NHC-catalyzed dynamic kinetic resolution of hydrophthalides

Scheme 9. NHC-catalyzed dynamic kinetic resolution of hemiaminals

Scheme 10. Synthesis of α-aryloxycarboxylic esters via NHC-catalyzed dynamic kinetic resolution

Scheme 11. Catalytic N-acylation of 3,4-dihydropyrimidin-2-(1H)-ones with enals

Scheme 12. Hydrogen bonding assisted kinetic resolution of acyclic β-hydroxy amides

Scheme 13. Post-aldol stereochemistry control and formation of quaternary stereogenic centers

Scheme 14. Dynamic kinetic resolution to access axially chiral amino esters

Scheme 15. Dynamic kinetic resolution of sulfoxides

Scheme 16. Kinetic resolution of α-hydroxythioamides

Scheme 17. Kinetic resolution of α-hydroxyamides

Scheme 18. Dynamic kinetic resolution of hydroxyphthalides using electroredox method

Scheme 19. NHC-catalyzed intermolecular all-carbon [4＋2] annulation

Scheme 20. Kinetic resolution of Michael adducts by Enders et al.

Scheme 21. -1 Dynamic kinetic resolution of enamines

Scheme 21. -2 Classical kinetic resolution of disubstituted imines

Scheme 22. Kinetic resolution of various α-functionalized ketones

Scheme 23. One-step separation of racemic mixtures of four stereoisomers

Scheme 24. Synthesis of cis- and trans-HDNDs

Scheme 25. Kinetic resolution of α,α-disubtituted β-ketoesters

Scheme 26. Classical kinetic resolution and divergent reaction of 1,3-diketones

Scheme 27. Construction of tetrahydrochromeno[3,4-b]chromenes by dynamic kinetic resolution

Scheme 28. Total synthesis of 12a-hydroxymunduserone, tephrosin, milletosin and 12a-hydroxyrotenone

Scheme 29. Atroposelective synthesis of axially chiral benzonitriles

Scheme 30. Dynamic kinetic resolution of acyclic ketoacids

Scheme 31. Dynamic kinetic asymmetric transformation of cyclopropylcarbaldehydes

Scheme 32. Kinetic resolution of secondary alcohols

Scheme 33. Synthesis of 2-aryl-3-nitro-2H-chromanes and its derivatives

Scheme 34. -1 Kinetic resolution and dynamic kinetic resolution of racemic N-tosylaziridines

Scheme 34. -2 Proposed mechanism for the kinetic resolution and dynamic kinetic resolution of racemic N-tosylaziridines

Scheme 35. β-Azolium ylide-participated kinetic resolution by Lupton et al.

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