Isosteviol-Type Organocatalysts in Asymmetric Catalysis over the Past Decade

doi:10.6023/cjoc202505008

Abstract

Isosteviol, the hydrolysate of stevioside, has attracted increasing attention from scientists because of its special molecular skeleton and extensive biological activities. In recent years, due to the continuous rise of organocatalysis, an increasing number of organocatalysts based on isosteviol have been devised and synthesized to facilitate a range of highly enantioselective asymmetric synthesis. The isosteviol-type organocatalysts reported in the literature over the past decade and their applications in asymmetric catalysis are systematically analyzed and elaborated in order to provide assistance for the further design, synthesis, and application of organocatalysis derived from isosteviol.

Key words: asymmetric catalysis, organocatalyst, isosteviol, bifunctional catalyst, thiourea, squaramide

Cite this article

Yuxia Liu, Congcong Li, Zhaoyang Fan, Qi Liu, Xinyu Dai. Isosteviol-Type Organocatalysts in Asymmetric Catalysis over the Past Decade[J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3613-3623.

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Fig. & Tab. 44

Figure 1. Isosteviol-type organocatalysts based on proline

Figure 2. Isosteviol-type isothiocyanates and squaramides

Figure 3. Isosteviol-derived bifunctional hydrogen bond donor organocatalysts

Scheme 1. Asymmetric Aldol condensation between cyclohexanone and aromatic aldehydes catalyzed by C1a

Scheme 2. Iisosteviol-type prolinamides catalyzed asymmetric Aldol reaction

Scheme 3. Enantioselective α-aminoxylation of ketones and aldehydes

Scheme 4. Enantioselective Mannich reaction of hydroxyacetone, aniline and benzaldehyde

Scheme 5. Enantioselective Mannich reactions of cyclohexanone, aniline and aromatic aldehyde

Figure 4. Hypothesized transition state of enantioselective Mannich reaction with C1b

Scheme 6. Enantioselective Michael reaction catalyzed by C3

Figure 5. Proposed intermediate of Michael reaction catalyzed by C3

Scheme 7. C4-catalyzed Michael addition of maleimide to aldehyde

Scheme 8. Michael addition of aldehyde to nitroalkene catalyzed by C4

Figure 6. Transition state structure of the S enantiomer

Figure 7. Transition state structure of the R enantiomer

Scheme 9. Michael reaction of maleimide with aldehyde catalyzed by C5

Scheme 10. C6-catalyzed Michael addition between acetylacetone and nitrooleﬁns

Figure 8. Potential transition-state of C6 catalyzed Michael addition

Scheme 11. C6a catalyzed conjugate addition between cyanoacetate and maleimides

Figure 9. A possible transition-state in addition reaction between cyanoacetate and maleimides

Scheme 12. C6 catalyzed enantioselective Michael/aromatize- tion reaction

Figure 10. Proposed transition state and mechanism

Scheme 13. Enantioselective Michael addition reaction catalyzed by C7a

Figure 11. Proposed catalytic transition-state in C7a catalyzed enantioselective Michael addition

Scheme 14. C8 catalyzed Michael addition of acetophenone to nitroalkene

Scheme 15. Enantioselective Michael addition reaction catalyzed by C9

Figure 12. Proposed transition-state in C9a catalyzed Michael addition

Scheme 16. C9 calatlyzed enantioselective Michael reaction

Figure 13. Proposed catalytic transition-state catalyzed by C9

Scheme 17. C10 catalyzed the Michael addition of isobutyraldehyde to maleimides

Figure 14. Possible transition-state of C10 catalyzing the Michael addition

Scheme 18. C9 catalyzed Michael addition of acetophenone to nitroalkenes

Figure 15. Proposed catalytic model of C9 catalyzing the Michael addition

Scheme 19. Asymmetric Michael addition catalyzed by C11a

Figure 16. Probable transition-state of C11a catalyzing the Michael addition

Scheme 20. Enantioselective Michael reaction catalyzed by C11b

Scheme 21. Michael addition reaction of nitroolefins and acetylacetone catalyzed by C11b

Figure 17. Probable transition-state of C11b catalyzing the Michael addition

Scheme 22. C11 catalyzing Michael addition of unsaturated α-keto esters to cyclic diketones

Figure 18. Possible transition-state of C11 catalyzing Michael addition

Scheme 23. Michael addition/cyclization reaction catalyzed by C12b

Scheme 24. Proposed transition state and mechanism

Scheme 25. Asymmetric Michael addition catalyzed by C12a

Figure 19. Probable transition-state of C12a catalyzing Michael addition

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过去十余年不对称催化中的异斯特维醇类有机催化剂