共轭烯酮的不对称双(转移)氢化研究进展

doi:10.6023/cjoc202603008

有机化学 ›› 2026, Vol. 46 ›› Issue (6): 2163-2176.DOI: 10.6023/cjoc202603008 上一篇下一篇

综述与进展

共轭烯酮的不对称双(转移)氢化研究进展

秦观宝^a^,^b, 赵梦龙^b, 韩召斌^b^,^*(), 丁奎岭^b^,^c^,^d^,^*()

^a 上海理工大学材料与化学学院上海 200093
^b 中国科学院上海有机化学研究所金属有机化学全国重点实验室上海 200032
^c 上海交通大学化学化工学院上海 200240
^d 上海交通大学变革性分子前沿科学中心上海 200240

收稿日期:2026-03-06 修回日期:2026-04-02 发布日期:2026-04-27
通讯作者: 韩召斌, 丁奎岭
基金资助:
国家重点研发计划(2021YFA1500200); 国家自然科学基金(21872167); 上海市优秀学术/技术带头人计划(22XD1424800)

Advances in Asymmetric Double (Transfer) Hydrogenation of Conjugated Enones

Guanbao Qin^a^,^b, Menglong Zhao^b, Zhaobin Han^b^,^*(), Kuiling Ding^b^,^c^,^d^,^*()

^a School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093
^b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
^c School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240
^d Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240

Received:2026-03-06 Revised:2026-04-02 Published:2026-04-27
Contact: Zhaobin Han, Kuiling Ding
Supported by:
National Key R&D Program of China(2021YFA1500200); National Natural Science Foundation of China(21872167); Program of Shanghai Academic/Technology Research Leader(22XD1424800)

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摘要/Abstract

共轭烯酮结构多样, 来源广泛, 其不对称双(转移)氢化是构建多手性中心仲醇的高效策略. 然而, 该转化需要催化体系还原两类性质不同的不饱和键, 并实现多重立体选择性的控制, 极具挑战. 近年来, 通过新配体和催化剂的发展、双金属接力催化体系的构建及添加剂调控催化过程等手段, 这一领域取得了显著进展. 从共轭烯酮的结构特点出发, 系统综述了过渡金属催化共轭烯酮不对称双氢化和不对称双转移氢化的研究进展, 并对当前领域存在的关键问题及未来发展方向进行了总结与展望.

关键词: 共轭烯酮, 不对称氢化, 不对称转移氢化, 过渡金属

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

引用此文

秦观宝, 赵梦龙, 韩召斌, 丁奎岭. 共轭烯酮的不对称双(转移)氢化研究进展[J]. 有机化学, 2026, 46(6): 2163-2176.

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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图/表 26

图式1. 共轭烯酮不对称催化双(转移)氢化的两条反应路径

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

图式2. 铑/钌催化的γ-酰氨基-γ,δ-不饱和β-酮酸酯的串联不对称双氢化

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

图式3. 铑/Duanphos催化的β-乙酰氨基共轭烯酮3的不对称双氢化

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

图式4. Ru-1催化的β-甲氨基-α,β-不饱和酮5的不对称双氢化

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

图式5. 钌催化的β-碳取代共轭烯酮7和11的不对称双氢化

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

图式6. 钌催化的β,γ-不饱和α-二酮14和α-羟基共轭烯酮19的不对称双转移氢化

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

图式7. Ru-6催化的β,β-双碳取代共轭烯酮20的不对称双氢化

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

图式8. 铑/L1催化的(E)-2-甲基-4-氧代-2-烯酸22的不对称双氢化

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

图式9. 铱催化α,β-双碳取代共轭烯酮24不对称双氢化

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

图式10. 双铱催化α,β-双碳取代共轭烯酮24的立体发散性不对称双氢化

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

图式11. Rh-1催化色酮27的不对称双转移氢化

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

图式12. Rh-2催化3-甲酰色酮29的不对称连续转移氢化

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

图式13. 钌/L2催化2-取代色酮33的不对称双氢化

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

图式14. RuPHOX-Ru催化2-烷基取代色酮33的不对称双氢化

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

图式15. 铑/f-spiroPhos催化2-三氟甲基色酮37的不对称双氢化

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

图式16. 铑/C10-BridgePhos催化3-氨基-4-色酮39的不对称双氢化

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

图式17. Rh-3催化环内共轭烯酮43的不对称双氢化

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

图式18. Ir-5催化四取代环内共轭烯酮45的不对称双氢化

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

图式19. Ru-7催化3,4-二取代环丁烯二酮的连续不对称转移氢化

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

图式20. 钌催化2,3-二芳基-4-烷基取代环丁烯酮54的连续不对称转移氢化

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

图式21. Ru-10和Rh-2催化环外共轭烯酮62的连续不对称转移氢化

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

图式22. 铱/L3催化共轭烯酮64, 66和68的不对称双氢化

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

图式23. Ru-11催化共轭烯酮64和70的不对称双氢化

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

图式24. 镍催化环外共轭烯酮64的不对称双氢化

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

图式25. Ru-12催化2-芳亚甲基-1,3-茚满二酮72的不对称转移氢化

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

图式26. Ir-6催化环状二烯酮75的连续不对称氢化

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

参考文献 42

[1]	Ratovelomanana-Vidal, V.; Phansavath, P. Asymmetric Hydrogenation and Transfer Hydrogenation, Wiley-VCH, Weinheim, 2021.
[2]	Tang, W.; Zhang, X. Chem. Rev. 2003, 103, 3029.
[3]	Xie, J.-H.; Zhu, S.-F.; Zhou, Q.-L. Chem. Rev. 2011, 111, 1713.
[4]	Zhang, Z.; Butt, N. A.; Zhang, W. Chem. Rev. 2016, 116, 14769.
[5]	Zhou, Q.-L. Privileged Chiral Ligands and Catalysts, Wiley-VCH, Weinheim, 2011.
[6]	de Vries, J. G.; Elsevier, C. J. Handbook of Homogeneous Hydrogenation, Vols. 1-3, Wiley, Weinheim, 2010.
[7]	Doi, T.; Kokubo, M.; Yamamoto, K.; Takahashi, T. J. Org. Chem. 1998, 63, 428.
[8]	Geng, H.; Zhang, W.; Chen, J.; Hou, G.; Zhou, L.; Zou, Y.; Wu, W.; Zhang, X. Angew. Chem., Int. Ed. 2009, 48, 6052.
[9]	Geng, H.; Huang, K.; Sun, T.; Li, W.; Zhang, X.; Zhou, L.; Wu, W.; Zhang, X. J. Org. Chem. 2011, 76, 332.
[10]	Huang, K.; Zhang, X.; Geng, H.; Li, S.-K.; Zhang, X. ACS Catal. 2012, 2, 1343.
[11]	Geng, H.; Zhang, X.; Chang, M.; Zhou, L.; Wu, W.; Zhang, X. Adv. Synth. Catal. 2011, 353, 3039.
[12]	Xue, D.; Chen, Y.-C.; Cui, X.; Wang, Q.-W.; Zhu, J.; Deng, J.-G. J. Org. Chem. 2005, 70, 3584.
[13]	Hall, T. H.; Adams, H.; Vysa, V. K.; Chu, M. K. L.; Wills, M. Tetra- hedron 2021, 77, 131771.
[14]	Demidoff, F. C.; Caleffi, G. S.; Figueiredo, M.; Costa, P. R. R. J. Org. Chem. 2022, 87, 14208.
[15]	Zhao, Z.; Dong, W.; Liu, J.; Yang, S.; Cotman, A. E.; Zhang, Q.; Fang, X. J. Am. Chem. Soc. 2024, 146, 33543.
[16]	Dong, W.; Ren, C.; Zhu, L.; Luo, P.; Zhao, Z.; Lan, S.; Liu, J.; Yang, S.; Zhang, Q.; Fang, X. ACS Catal. 2024, 14, 18753.
[17]	Arai, N.; Satoh, H.; Komatsu, R.; Ohkuma, T. Chem.-Eur. J. 2017, 23, 8806.
[18]	Liu, X.; Chen, C.; Yuan, H.; Tang, X.; Jiang, R.; Gao, Y.; Nie, H. Eur. J. Org. Chem. 2022, 2022, e202200673.
[19]	Peter, B. B. C.; Zheng, J.; Krajangsri, S.; Andersson, P. G. J. Am. Chem. Soc. 2022, 144, 8734.
[20]	Zheng, J.; Peter, B. B. C.; Mallick, R. K.; Andersson, P. G. Angew. Chem., Int. Ed. 2025, 64, e202415171.
[21]	Tang, L.; Lin, Z.; Wang, Q.; Wang, X.; Cun, L.; Yuan, W.; Zhu, J.; Deng, J. Tetrahedron Lett. 2012, 53, 3828.
[22]	He, B.; Phansavath, P.; Ratovelomanana-Vidal, V. Org. Lett. 2019, 21, 3276.
[23]	Zhao, D.; Beiring, B.; Glorious, F. Angew. Chem., Int. Ed. 2013, 52, 8454.
[24]	Ma, Y.; Li, J.; Ye, J.; Liu, D.; Zhang, W. Chem. Commun. 2018, 54, 13571.
[25]	Xu, S.; Xu, W.; Dong, S.; Liu, D.; Zhang, W. Chem.-Eur. J. 2024, 30, e202400978.
[26]	Xie, C.; Guo, Q.; Wu, X.; Ye, W.; Hou, G. J. Org. Chem. 2023, 88, 15726.
[27]	Xu, Y.; Luo, Y.; Ye, J.; Deng, Y. Liu, D.; Zhang, W. J. Am. Chem. Soc. 2022, 144, 20078.
[28]	Hu, Q.; Chen, J.; Zhang, Z.; Liu, Y.; Zhang, W. Org. Lett. 2016, 18, 1290.
[29]	Liu, Y.-T.; Chen, J.-Q.; Li, L.-P.; Shao, X.-Y.; Xie, J.-H.; Zhou, Q.-L. Org. Lett. 2017, 19, 3231.
[30]	Liu, Y.-T.; Li, L.-P.; Xie, J.-H.; Zhou, Q.-L. Angew. Chem., Int. Ed. 2017, 56, 12708.
[31]	Li, L.-P.; Han, J.-Q.; Liu, Y.-T.; Yang, F.; Wu, X.; Xie, J.-H.; Zhou, Q.-L. Org. Lett. 2022, 24, 2590.
[32]	Li, L.-P.; Han, J.-Q.; Yang, F.; Wu, X.; Xie, J.-H.; Zhou, Q.-L. Org. Lett. 2022, 24, 3477.
[33]	Lan, S.; Huang, H.; Liu, W.; Xu, C.; Lei, X.; Dong, W.; Liu, J.; Yang, S.; Cotman, A. E.; Zhang, Q.; Fang, X. J. Am. Chem. Soc. 2024, 146, 4942.
[34]	Lan, S.; Luo, Y.; Jiang, C.; Xu, C.; Zhao, L.; Lei, X.; Dong, J.; Liu, J.; Yang, S.; Zhang, Q.; Fang, X. Angew. Chem., Int. Ed. 2025, 64, e202512543.
[35]	Caleffi, G. S.; Brum, J. d. O. C.; Costa, A. T.; Domingos, J. L. O.; Costa, P. R. R. J. Org. Chem. 2021, 86, 4849.
[36]	Betancourt, R. M.; Phansavath, P.; Ratovelomanana-Vidal, V. Org. Lett. 2021, 23, 1621.
[37]	Li, W.; Yang, T.; Song, N.; Li, R.; Long, J.; He, L.; Zhang, X.; Lv, H. Chem. Sci. 2022, 13, 1808.
[38]	Wang, K.; Niu, S.; Tang, W.; Xue, D.; Xiao, J.; Li, H.; Wang, C. Chem. Commun. 2024, 60, 4338.
[39]	Wang, K.; Niu, S.; Guo, X.; Tang, W.; Xue, D.; Xiao, J.; Sun, H.; Wang, C. J. Org. Chem. 2022, 87, 3804.
[40]	Liu, Y.; Yang, C.; Zuo, L.; Liu, Q.; Zhang, X.; Hou, C.; Yin, C.; Zhou, H. Org. Lett. 2025, 27, 4183.
[41]	Li, J.; Tang, J.; Song, H.; Xu, Z.; Chen, S.; Liu, Y.; Yang, J.; Wen, X.; Lu, Z.; Lv, J.; Xiao, H.; Long, J.; Mo, X.; Song, J.; Zhang, B.; Shao, P.-L. Adv. Sci. 2025, e17370.
[42]	Peter, B. B. C.; Zheng, J.; Zhang, H.; Andersson, P. G. Org. Lett. 2026, 28, 106.

共轭烯酮的不对称双(转移)氢化研究进展

Advances in Asymmetric Double (Transfer) Hydrogenation of Conjugated Enones

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