Advances in Asymmetric Double (Transfer) Hydrogenation of Conjugated Enones

doi:10.6023/cjoc202603008

Abstract

Conjugated enones feature diverse structures and wide availability. Their asymmetric double (transfer) hydrogenation serves as an efficient strategy for the construction of secondary alcohols with multiple chiral centers. However, such transformations are highly challenging, as it requires the catalytic system to reduce two distinct types of unsaturated bonds while achieving precise control over multiple stereoselectivities. In recent years, remarkable progress has been made in this field through the development of new ligands and catalysts, the utilization of bimetallic relay catalytic systems, and the regulation of catalytic processes by additives. Based on the structural characteristics of conjugated enones, the advances in transition-metal-catalyzed asymmetric double hydrogenation and asymmetric double transfer hydrogenation of conjugated enones are summarized. The key challenges and future prospects in this area are also outlined and discussed.

Key words: conjugated enone, asymmetric hydrogenation, asymmetric transfer hydrogenation, transition metal

Cite this article

Guanbao Qin, Menglong Zhao, Zhaobin Han, Kuiling Ding. Advances in Asymmetric Double (Transfer) Hydrogenation of Conjugated Enones[J]. Chinese Journal of Organic Chemistry, 2026, 46(6): 2163-2176.

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Fig. & Tab. 26

Scheme 1. Two reaction paths for the asymmetric double (trans- fer) hydrogenation of conjugated enones

Scheme 2. Rh/Ru dual catalyzed sequential asymmetric double hydrogenation of γ-(acylamino)-γ,δ-unsaturated-β-keto esters

Scheme 3. Rh/Duanphos catalyzed asymmetric double hydrogenation of β-acetamido conjugated enones 3

Scheme 4. Ru-1 catalyzed asymmetric double hydrogenation of β-methylamino-α,β-unsaturated ketones 5

Scheme 5. Ruthenium-catalyzed asymmetric double transfer hydrogenation of β-carbon-substituted conjugated enones 7 and 11

Scheme 6. Ruthenium-catalyzed asymmetric double transfer hydrogenation of β,γ-unsaturated α-diketones 14 and α-hydroxyenones 19

Scheme 7. Ru-6 catalyzed asymmetric double hydrogenation of β,β-dicarbon-substituted conjugated enones 20

Scheme 8. Rh/L1 catalyzed asymmetric double hydrogenation of (E)-2-methyl-4-oxo-2-alkenoic acids 22

Scheme 9. Iridium catalyzed asymmetric double hydrogenation of α,β-dicarbon-substituted conjugated enones 24

Scheme 10. Ir/Ir dual catalyzed stereodivergent asymmetric double hydrogenation of α,β-dicarbon-substituted conjugated enones 24

Scheme 11. Rh-1 catalyzed asymmetric double transfer hydrogenation of chromenones 27

Scheme 12. Rh-2 catalyzed sequential asymmetric transfer hydrogenation of 3-formylchromones 29

Scheme 13. Ru/L2 catalyzed Asymmetric double hydrogenation of 2-substituted chromones 33

Scheme 14. RuPHOX-Ru catalyzed asymmetric double hydrogenation of 2-alkyl-chromones 33

Scheme 15. Rh/f-spiroPhos catalyzed asymmetric double hydrogenation of 2-CF3-chromenones 37

Scheme 16. Rh/C10-BridgePhos catalyzed asymmetric double hydrogenation of 3-amino-4-chromanones 39

Scheme 17. Rh-3 catalyzed asymmetric double hydrogenation of endocyclic conjugated enones 43

Scheme 18. Ir-5 catalyzed asymmetric double hydrogenation of tetrasubstituted endocyclic conjugated enones 45

Scheme 19. Ru-7 catalyzed sequential asymmetric transfer hydrogenation of 3,4-disubstituted cyclobutenediones 49

Scheme 20. Ruthenium catalyzed sequential asymmetric transfer hydrogenation of 2,3-diaryl-4-alkyl-cyclobutenones 54

Scheme 21. Ru-10 and Rh-2 catalyzed sequential asymmetric transfer hydrogenation of exocyclic conjugated enones 62

Scheme 22. Ir/L3 catalyzed asymmetric double hydrogenation of sequential hydrogenation of conjugated enones 64, 66 and 68

Scheme 23. Ru-11 catalyzed asymmetric double hydrogenation of conjugated enones 64 and 70

Scheme 24. Nickel catalyzed asymmetric double hydrogenation of exocyclic conjugated enones 64

Scheme 25. Ru-12 catalyzed asymmetric transfer hydrogenation of 2-arylidene-1,3-indandiones 72

Scheme 26. Ir-6 catalyzed sequential asymmetric hydrogenation of cyclic dienones 75

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