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Review
. 2023 Oct 24;13(44):31047-31058.
doi: 10.1039/d3ra06715g. eCollection 2023 Oct 18.

Dehydroabietane-type bifunctional organocatalysts in asymmetric synthesis: recent progress

Affiliations
Review

Dehydroabietane-type bifunctional organocatalysts in asymmetric synthesis: recent progress

Zhen-Wei Zhang et al. RSC Adv. .

Abstract

Dehydroabietane-type bifunctional organocatalysts derived from rosane-type diterpenes of dehydroabietic acid (DHAA) and dehydroabietylamine (DA) have been utilized in a wide variety of highly enantioselective reactions. Since one well-documented review exclusively reported on the development of terpene-derived bifunctional thioureas in asymmetric organocatalysis in 2013, fragmentary progress on the dehydroabietane-type bifunctional thioureas and squaramides has been mentioned in other reviews. In this mini-review, we systematically analyze and reorganize the published literature on dehydroabietane-type bifunctional organocatalysts in the recent decade according to the type of catalysts. Our aim is for this review to provide helpful research information and serve as a foundation for further design and application of rosin-based organocatalysts.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Abietic and dehydroabietic acid derivatives.
Fig. 2
Fig. 2. Dehydroabietane-type bifunctional organocatalysts described in this review.
Scheme 1
Scheme 1. Asymmetric Michael addition of nitroalkanes to α,β-unsaturated ketones.
Scheme 2
Scheme 2. Asymmetric Michael addition of α,α-disubstituted aldehydes and β-nitroalkenes.
Scheme 3
Scheme 3. Asymmetric Michael addition of (hetero)aromatic ketones to nitrodienes.
Scheme 4
Scheme 4. Asymmetric aza-Henry reaction of nitroalkanes and α-amidosulfones.
Scheme 5
Scheme 5. Asymmetric Mannich reaction of lactones and N-Boc-aldimines.
Fig. 3
Fig. 3. Ternary complex A.
Scheme 6
Scheme 6. Asymmetric 1,3-dipolar cycloaddition reaction of homoserine lactone derived cyclic imino esters and methyleneindolinones.
Scheme 7
Scheme 7. Asymmetric IEDDA reaction of 2-nitrocycloketones and β,γ-unsaturated α-ketone esters.
Fig. 4
Fig. 4. A possible transition-state model.
Scheme 8
Scheme 8. Asymmetric IEDDA reaction of α,β-unsaturated γ-butyrolactams.
Fig. 5
Fig. 5. A possible transition-state model of the β,γ-selective IEDDA reaction.
Scheme 9
Scheme 9. Asymmetric IEDDA/Henry inverse reaction of α-nitroketones and β,γ-unsaturated α-ketone esters.
Scheme 10
Scheme 10. Asymmetric Michael/cyclization of α-hydroxyimino cyclic ketones to β,γ-unsaturated α-keto esters.
Fig. 6
Fig. 6. A possible transition-state model of the asymmetric Michael/cyclization.
Scheme 11
Scheme 11. Asymmetric Michael/cyclization of 3-isothiocyanato oxindoles to unsaturated pyrazolones.
Scheme 12
Scheme 12. Asymmetric Michael/cyclization of α,α-dicyanoalkenes to 3-alkylideneoxindoles.
Fig. 7
Fig. 7. A possible transition-state model of the asymmetric Michael/cyclization.
Scheme 13
Scheme 13. Asymmetric Michael/cyclization of 3-isothiocyanato oxindoles to electron-deficient olefins.
Scheme 14
Scheme 14. Asymmetric Michael addition of 2-hydroxy-1,4-naphthoquinone to β-nitroalkenes.
Fig. 8
Fig. 8. A possible transition-state model of the asymmetric Michael reaction.
Scheme 15
Scheme 15. Asymmetric Michael addition of 1,3-dicarbonyl compounds to β-nitroalkenes.
Scheme 16
Scheme 16. Asymmetric Michael/hemiketalization of kojic acid derivatives to β,γ-unsaturated α-ketone esters.
Scheme 17
Scheme 17. Asymmetric allylic amination of phthalimide and Morita–Baylis–Hillman acetates.
Fig. 9
Fig. 9. A possible transition-state model of the asymmetric MBH reaction.
Scheme 18
Scheme 18. Asymmetric heterogeneous Mannich reaction of dibenzyl malonate and α-amidosulfones.
Scheme 19
Scheme 19. Asymmetric heterogeneous IEDDA reaction of azlactones and multisubstituted dicyano-2-methylenebut-3-enoates.
Scheme 20
Scheme 20. Asymmetric domino reaction of 4-hydroxy-2H-chromen-2-ones and methylene malononitriles.
Scheme 21
Scheme 21. Asymmetric Michael/cyclization of 3-isothiocyanato oxindoles to (E)-3-arylidenechroman-4-ones.
Fig. 10
Fig. 10. A possible transition-state model.
Scheme 22
Scheme 22. Asymmetric Michael addition of malononitrile to α,β-unsaturated ketones.
Fig. 11
Fig. 11. Proposed model of nucleophilic attack.

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