铁系金属催化烯烃不对称氢化反应的研究进展

doi:10.6023/cjoc202602021

摘要/Abstract

过渡金属催化前手性烯烃不对称氢化反应是构建手性化合物的重要方法之一,因操作简便、后处理容易及原子经济性高等特点而备受关注。主要依赖钌、铑、铱、钯等贵金属催化体系,然而这些金属资源有限、成本高昂,且存在潜在环境风险。为此,过去数十年间,研究者致力于发展以铁、钴、镍为代表的地球储量高、低毒/无毒且环境友好的廉价铁系金属催化体系,并在不对称氢化领域取得了一系列重要突破。本文简要评述近年来铁系金属铁、钴、镍催化烯烃（C=C）不对称氢化反应研究进展,深入分析该类催化体系在底物适用范围、催化效率与选择性等方面的优势与不足。相关研究尽管已取得显著进展,仍面临诸多挑战,包括反应机理尚不明晰、高效手性配体匮乏等。未来亟需开发结构新颖、易于合成的手性配体,并探索更具普适性的催化体系。

关键词: 不对称氢化, 丰产金属, 烯烃, 手性化合物, 立体选择性

Transition metal-catalyzed asymmetric hydrogenation of prochiral alkenes is an important method for the construction of chiral compounds, and has garnered great attention due to its operational simplicity, ease of work-up, and high atom economy. It mainly relied on noble metal catalytic systems such as ruthenium, rhodium, iridium, and palladium. However, these metals suffer from limited resources, high costs, and potential environmental risks. Therefore, over the past few decades, researchers have focused on the development of catalytic systems based on earth-abundant, low- or non-toxic, and environmentally friendly iron-group metals, including iron, cobalt, and nickel. Significant breakthroughs have been achieved in the field of asymmetric hydrogenation using these metals. This article briefly reviews the recent progress in iron-group metal (Fe, Co, Ni)-catalyzed asymmetric hydrogenation of alkenes (C=C), and provides an in-depth analysis of the advantages and limitations of these catalytic systems in terms of substrate scope, catalytic efficiency, and selectivity. Although remarkable progress has been made, the field still faces some challenges, including unclear reaction mechanisms and a lack of efficient chiral ligands. Future efforts should focus on the development of new, easily accessible chiral ligands and exploring more universal catalytic systems.

Key words: asymmetric hydrogenation, earth-abundant transition metals, olefins, chiral compounds, stereoselectivity

引用此文

余品科, 刘海阳, 肖帆, 董秀琴. 铁系金属催化烯烃不对称氢化反应的研究进展[J]. 有机化学, doi: 10.6023/cjoc202602021.

Yu Pinke, Liu Haiyang, Fan Xiao, Dong Xiu-Qin. Recent Progress on Iron-Group Metal-Catalyzed Asymmetric Hydrogenation of Alkenes[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202602021.

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参考文献

[1] (a) Xie J. H.; Zhu S. F.; Zhou, Q. L. Chem. Rev.2011, 111, 1713.
(b) Wang Y.; Zhang Z.; Zhang, W. Chin. J. Org. Chem.2015, 35, 528 (in Chinese).
(王英杰, 张振锋, 张万斌, 有机化学, 2015, 35#, 528.).
(c) Wang, D.-S.; Chen, Q.-A.; Lu, S.-M.; Zhou, Y.-G. Chem. Rev#. 2012, 112#, 2557.
[2] (a) Liang, Z.; Yang, T.; Gu, G.; Dang, L.; Zhang, X. Chin. J. Chem. 2018, 36, 851 (in Chinese).
(梁志钦, 杨题隆, 古国贤, 党丽, 张绪穆, 中国化学, 2018, 36, 851.).
(b) Zhang, Z.; Butt, N. A.; Zhou, M.; Liu, D.; Zhang, W.Chin. J. Chem. 2018, 36, 443 (in Chinese).
(张振锋, Nicholas Andrew Butt, 周牧星, 刘德龙, 张万斌, 中国化学, 2018, 36#, 443.).
[3] (a) Morris, R. H. Acc. Chem. Res.2015, 48, 1494.
(b) Chirik, P. J. Acc. Chem. Res.2015, 48, 1687.(c) Li, Y.-Y.; Yu, S.-L.; Shen, W.-Y.; Gao, J.-X. Acc. Chem. Res. 2015, 48, 2587.
[4] Viereck P.; Rummelt S. M.; Soja N. A.; Pabst T. P.; Chirik P. J. Organometallics.2021, 40, 1053-1061.
[5] Lu P.; Ren X.; Xu H.; Lu D.; Sun Y.; Lu, Z. J. Am. Chem. Soc.2021, 143, 12433-12438.
[6] Monfette S.; Turner Z. R.; Semproni, S P.; Chirik, P. J. J. Am. Chem. Soc.2012, 134, 4561-4564.
[7] Friedfeld M. R.; Shevlin M.; Hoyt J. M.; Kraska S. W.;Tudge M. T.; Chirik P. J. Science2013, 342, 1076-1079.
[8] Friedfeld M. R.; Shevlin M.; Margulieux G. W.; Campeau L.-C.; Chirik, P. J. J. Am. Chem. Soc.2016, 138, 3314-3324.
[9] Friedfeld M. R.; Zhong H.; Ruck R. T.; Shevlin M.; Chirik P. J. Science2018, 360, 888-893.
[10] Zhong H.; Shevlin M.; Chirik, P. J. J. Am. Chem. Soc.2020, 142, 5272-5281.
[11] Viereck P.; Krautwald S.; Pabst T. P.; Chirik, P. J. J. Am. Chem. Soc.2020, 142, 3923-3930.
[12] Mendelsohn L. N.;MacNeil, C. S.; Esposito, M. R.; Pabst, T. P.; Leahy, D. K.; Davies, I. W.; Chirik, P. J. Org. Lett. 2024, 26, 2718-2723.
[13] Chen J.; Chen C.; Ji C.; Lu Z.Org. Lett. 2016, 18, 1594-1597.
[14] Guo J.; Shen X.; Lu, Z. Angew. Chem. Int. Ed.2017, 56, 615-618.
[15] Guo J.; Cheng B.; Shen X.; Lu, Z. J. Am. Chem. Soc.2017, 139, 15316-15319.
[16] Ren X.; Lu Z. Org. Lett.2021, 23, 8370-8374.
[17] Lu P.; Wang H.; Mao Y.; Hong X.; Lu, Z. J. Am. Chem. Soc.2022, 144, 17359-17364.
[18] Zuo Z.; Xu S.; Zhang L.; Gan L.; Fang H.; Liu G.; Huang Z. Organometallics.2019, 38, 3906-3911.
[19] Du X.; Xiao Y.; Huang J.; Zhang Y.; Duan Y.; Wang H.; Shi C.; Chen G.; Zhang X. Nat. Commun.2020, 11, 3239.
[20] Du X.; Xiao Y.; Yang Y.; Duan Y.; Li F.; Hu Q.; Chung L.; Chen G.; Zhang, X. Angew. Chem. Int. Ed.2021, 60, 11384-11390.
[21] Hu Y.; Zhang Z.; Liu Y.; Zhang, W. Angew. Chem. Int. Ed.2021, 60, 16989-16993.
[22] Hu Y.; Zou Y.; Yang H.; Ji H.; Jin Y.; Zhang Z.; Liu Y.; Zhang, W. Angew. Chem. Int. Ed.2023, 62, e202217871.
[23] Jin Y.; Zou Y.; Hu Y.; Han Y.; Zhang Z.; Zhang, W. Chem. Eur. J.2022, 28, e202201517.
[24] Chen T.; Zou Y.; Hu Y.; Zhang Z.; Wei H.; Wei L.; Zhang, W. Angew. Chem. Int. Ed.2023, 62, e202303488.
[25] Chakrabortty S.; Konieczny K.; de Zwart F. J.; Bobylev E. O.; Barath E.; Tin S.; Müller B. H.; Reek J. N. H.; de Bruin B.; de Vries, J. G. Angew. Chem. Int. Ed.2023, 62, e202301329.
[26] Chakrabortty S.; de Zwart F. J.; Snabilie D. D.; Balaraman E.; Reek J. N. H.; de Bruin B.; de Vries, J. G. Catal. Sci. Technol.2023, 13, 6668-6674.
[27] Li A.; Song X.; Ren Q.; Bao P.; Long X.; Huang F.; Yuan L.; Zhou J.; Qin, X. Angew. Chem. Int. Ed.2023, 62, e202301091.
[28] Yang P.; Xu H.; Zhou, J. Angew. Chem. Int. Ed.2014, 53, 12210-12213.
[29] Guo S.; Yang P.; Zhou J. Chem. Commun.2015, 51, 12115-12118.
[30] Guo S.; Zhou J. Org. Lett.2016, 18, 5316-5319.
[31] Shevlin M.; Friedfeld M. R.; Sheng H.; Pierson N. A.; Hoyt J. M.; Campeau L.C.; Chirik, P. J. J. Am. Chem. Soc.2016, 138, 3562-3569.
[32] Gao W.; Lv H.; Zhang T.; Yang Y.; Chung L. W.; Wu Y.; Zhang X. Chem. Sci.2017, 8, 6419-6422.
[33] Li X.; You C.; Li S.; Lv H.; Zhang X. Org. Lett.2017, 19, 5130-5133.
[34] Long J.; Gao W.; Guan Y.; Lv H.; Zhang X. Org. Lett.2018, 20, 5914-5917.
[35] Han Z.; Liu G.; Zhang X.; Li A.; Dong X.; Zhang X. Org. Lett.2019, 21, 3923-3926.
[36] Guan Y.; Han Z.; Li X.; You C.; Tan X.; Lv H.; Zhang X. Chem. Sci.2018, 9, 4890-4894.
[37] You C.; Li X.; Gong Q.; Wen J.; Zhang, X. J. Am. Chem. Soc.2019, 141, 14560-14564.
[38] Hu Y.; Chen J.; Li B.; Zhang Z.; Gridnev I. D.; Zhang, W. Angew. Chem. Int. Ed.2020, 59, 5371-5375.
[39] Guo S.; Wang X.; Zhou, J. S. Org. Lett.2020, 22, 1204-1207.
[40] Liu Y.; Yi Z.; Yang X.; Wang H.; Yin C.; Wang M.; Dong X.; Zhang X.ACS Catal. 2020, 10, 11153-11161.
[41] Liu G.; Tian K.; Li C.; You C.; Tan X.; Zhang H.; Zhang X.; Dong X. Org. Lett. 2021, 23, 668-675.
[42] Zhou J. S.; Guo S.; Zhao X.; Chi, Y. R. Chem. Commun.2021, 57, 11501-11504.
[43] Xiao G.; Xie C.; Guo Q.; Zi G.; Hou G.; Huang Y.Org. Chem. Front. 2022, 9, 4472-4477.
[44] Sudhakaran S.; Shinde P. G.; Aratikatla E. K.; Kaulage S. H.; Rana P.; Parit R. S.; Kavale D. S.; Senthilkumar B.; Punji B.Chem. Asian J. 2022, 17, e202101208.
[45] Wei H.; Chen H.; Chen J.; Gridnev I. D.; Zhang, W. Angew. Chem. Int. Ed.2023, 62, e202214990.
[46] Yang X.; Liu G.; Xiang X.; Xie D.; Han J.; Han Z.; Dong X. Org. Lett.2023, 25, 738-743.
[47] Sun Y.; Wang C.; Yang P.; Yue J.; Xu C.; Zhou J. S.; Tang B. ACS Catal.2023, 13, 14213-14220.
[48] Liu G.; Yang X.; Gu P.; Wang M.; Zhang X.; Dong X.J. Am. Chem. Soc. 2024, 146, 7419-7430.
[49] Li B.; Wang Z.; Luo Y.; Wei H.; Chen J.; Liu D.; Zhang W. Nat. Commun.2024, 15, 5482.
[50] Wei H.; Luo Y.; Li J.; Chen J.; Gridnev I. D.; Zhang W.J. Am. Chem. Soc. 2025, 147, 342-352.
[51] Cai X.; Luo Y.; Chen J.; Zhang, W. J. Am. Chem. Soc.2025, 147, 342-352.
[52] Li M.; Peters, J. C. ACS Catal.2025, 15, 13720-13726.
[53] Liu Y.; Yang C.; Zuo L.; Liu Q.; Zhang X.; Hou C.; Yin C.; Zhou H. Org. Lett.2025, 27, 4183-4189.