Abundant metals (such as iron, cobalt, nickel, copper, zinc, and manganese) have prominent advantages including rich reserves, low cost, environmental friendliness, mild reaction conditions, and few by-products. Their asymmetric catalysis has become a core research direction to replace precious metals such as palladium, rhodium, and iridium. Developed by the Junliang Zhang research group in 2014 based on the design concepts of non-C₂ symmetry, rigidity combined with flexibility, and containing multiple coordinating atoms such as P, N, O, and S, Sadphos ligands are a new type of chiral phosphine ligands with chiral tert-butylsulfinamide as the core skeleton. They have been developed into multiple series including Ming-Phos, Wei-Phos,Xiang-Phos, Xu-Phos, PC-Phos, TY-Phos, W-Phos, WJ-Phos, etc, featuring diverse structures, easy modification, abundant coordination sites, and excellent stereoregulatory ability. In 2016, Sadphos ligands were first applied in asymmetric abundant metal catalytic reactions, opening a new chapter in the research on the combination of the two. This review systematically summarizes the research progress of Sadphos ligands in asymmetric reactions and polymerization reactions catalyzed by abundant metals (such as copper, nickel, and cobalt) over the past ten years from 2016 to 2026. Classified by the type of abundant metals, it focuses on summarizing their applications in various reactions including [3+2] cycloaddition, asymmetric addition, asymmetric cross-coupling, asymmetric borylation of 1,1-disubstituted allenes, reductive cyclization, dynamic kinetic reductive conjugate addition, axially chiral construction, enantioselective addition/vinylation of sulfinimines, and polymerization of allene monomers. It also discusses the matching between ligand structure and metal center as well as the stereoregulatory mechanism of catalysis, analyzes the challenges faced in current research, and looks forward to future development directions, providing references for further research, structural innovation, and industrial application in this field.
Zhang Ruinan
,
Zheng Qizhi
,
Lai Shengyi
,
Luo Wenjun
,
Xu Bing
,
Zhang Zhan-Ming
,
Zhang Junliang
. Applications of Sadphos in Earth-Abundant Metal Catalysis[J]. Chinese Journal of Organic Chemistry, 0
: 202604047
.
DOI: 10.6023/cjoc202604047
[1] 林国强,李月明,陈耀全,孙兴文,陈新滋. 手性合成——不对称反应及其应用. 科学出版社,北京,2010.
[2] 麻生明. 金属有机参与的现代有机合成化学. 广东科技出版社, 广州, 2003.
[3] Nozaki H.; Moriuti S.; Takaya H.; Noyiri R. Tetrahedron Lett.1966, 7, 5239.
[4] Knowles W. S.; Sabacky M. J.; Vineyard, B. D. J. Chem. Soc. Chem. Commun.1972, 10.
[5] Noyori, R. Science1990, 248, 1194.
[6] Klunder J. M.; Onami T.; Sharpless, K. B. J. Org. Chem.1989, 54, 1295.
[7] Liu X.-Y.; Qin, Y. Green Synth. Catal.2022, 3, 25.
[8] Liu H.; Deng Y.; Ling D.; Chen L.; Jin, Z. Chin. Chem. Lett.2026, 37, 111793.
[9] Fürstner, A. ACS Cent. Sci.2016, 2, 778.
[10] Liu Y.; You T.; Wang H.-X.; Tang Z.; Zhou C.-Y.; Che, C.-M. Chem. Soc. Rev.2020, 49, 5310.
[11] Yang, M.; Liu, Y.; Qi, X.; Zhao, Y.; Wu, X.-F.Green Synth. Catal. 2024, 5, 211.
[12] Das A. K.; Sarkar K.; Bhattacharjee S.; Gajurel S.; Dhibar S.; Panja S. K.; Deshmukhf S. A.; Sarkar S. RSC Adv.2026, 16, 19920.
[13] Zhou T.; Yang H.; Zhou G.; Chen F.; Gao, P. Chin. Chem. Lett.2026, 37, 112223.
[14] Liu Y.; Li W.; Zhang, J. Natl. Sci. Rev.2017, 4, 326.
[15] Li W.; Zhang, J. Acc. Chem. Res.2024, 57, 489.
[16] Zhang Z.-M.; Chen P.; Li W.; Niu Y.; Zhao X.; Zhang, J. Angew. Chem. Int. Ed.2014, 53, 4350.
[17] Zhang Z.-M.; Xu B.; Xu S.; Wu H.-H.; Zhang, J. Angew. Chem. Int. Ed.,2016, 128, 6432.
[18] Xu B.; Zhang Z.-M.; Xu S.; Liu B.; Xiao Y.; Zhang J. ACS Catal.,2016, 7, 210.
[19] Liu, B.; Zhang, Z.-M., Xu, B.; Xu, S.; Wu, H.-H.; Zhang, [J].Adv. Synth. Catal., 2018, 360, 2144.
[20] Zhang R.; Xu B.; Zhang Z.; Zhang, J. Acta Chim. Sinica,2020, 78, 245. 张荣华;许冰;张展鸣;张俊良. 化学学报, 2020, 78, 245.
[21] Luo W.; Zhang L.-M.; Zhang Z.-M.; Zhang, J. Angew. Chem. Int. Ed.,2022, 61, e202204443.
[22] Zhang L.-M.; Luo W.; Fu J.; Liu Y.; Zhang J. ACS Catal.,2023, 13, 8830.
[23] Shi Y.; Yuan Y.; Li J.; Yang J.; Zhang, J. J. Am. Chem. Soc.,2024, 146, 17580.
[24] Yuan Y.; Pan L.; Han Y.; Tian X.; Ye W.; Zhang J.; Yang J. CCS Chem.2026, 8, 2206.
[25] Han J.; Zhou W.; Zhang P.-C.; Wang H.; Zhang R.; Wu H.-H.; Zhang J. ACS Catal.,2019, 9, 6890.
[26] Kang S.-M.; Xu X.-H.; Xu L.; Zhou L.; Liu N.; Wu Z.-Q. Polym. Chem.,2021, 12, 4822.
[27] Pan Q.; Wang K.; Xu W.; Ai Y.; Ping Y.; Liu C.; Kong, W. J. Am. Chem. Soc.,2024, 146, 15453.
[28] Xu X.-Y.; Liu L.-G.; Xu L.-C.; Zhang S.-Q.; Hong, X. J. Am. Chem. Soc.,2025, 147, 15318.
[29] Xiong W.; Jiang X.; Wang W.-C.; Cheng Y.; Lu L.-Q.; Gao K.; Xiao, W.-J. J. Am. Chem. Soc.,2023, 145, 7983.