Sadphos在丰产金属催化反应中的应用

doi:10.6023/cjoc202604047

有机化学 ›› 2026, Vol. 46 ›› Issue (9): 3390-3398.DOI: 10.6023/cjoc202604047 上一篇下一篇

综述与进展

Sadphos在丰产金属催化反应中的应用

张瑞楠^a, 郑琪智^d, 赖圣怡^e, 罗文俊^a^,^*(), 许冰^b^,^*(), 张展鸣^c^,^*(), 张俊良^c^,^*()

^a 赣南师范大学化学与材料科学学院江西赣州 341000
^b 海军军医大学药学系上海 200433
^c 复旦大学化学系上海 200438
^d 华东理工大学药学院上海 200237
^e 东华大学化学与化工学院上海 201620

收稿日期:2026-04-28 修回日期:2026-05-25 发布日期:2026-07-23
基金资助:
国家自然科学基金(22501294); 国家自然科学基金(22308061); 上海市东方英才计划(QNKJ2025050); 江西省自然科学基金(20243BCE51174); 江西省自然科学基金(20242BAB20110)

Applications of Sadphos in Earth-Abundant Metal Catalysis

Ruinan Zhang^a, Qizhi Zheng^d, Shengyi Lai^e, Wenjun Luo^a^,^*(), Bing Xu^b^,^*(), Zhan-Ming Zhang^c^,^*(), Junliang Zhang^c^,^*()

^a College of Chemistry and Materials Science, Gannan Normal University, Ganzhou, Jiangxi 341000
^b School of Pharmacy, Naval Medical University, Shanghai 200433
^c Department of Chemistry, Fudan University, Shanghai 200438
^d School of Pharmacy, East China University of Science and Technology, Shanghai 200237
^e College of Chemistry and Chemical Engineering, Donghua University, Shanghai 201620

Received:2026-04-28 Revised:2026-05-25 Published:2026-07-23
Contact:
^* E-mail: wenjunluo@gnnu.edu.cn;
^* E-mail: wenjunluo@gnnu.edu.cn;
xubing_0520@163.com;
zhanmingzhang@fudan.edu.cn;
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
Supported by:
National Natural Science Foundation of China(22501294); National Natural Science Foundation of China(22308061); Shanghai Oriental Talents Program(QNKJ- 2025050); Natural Science Foundation of Jiangxi Province(20243BCE51174); Natural Science Foundation of Jiangxi Province(20242BAB20110)

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摘要/Abstract

丰产金属(铁、钴、镍、铜、锌和锰等)因储量丰富、成本低廉、环境友好、反应条件温和及副产物少等优势, 其不对称催化已成为替代钯、铑或铱等贵金属的核心研究方向. Sadphos配体是张俊良课题组于2014年基于非C₂对称, 刚柔并济及含P、N、O和S等多配位原子的设计理念开发的新型手性膦配体, 以手性叔丁基亚磺酰胺为核心骨架, 目前已发展出Ming-Phos、Wei-Phos、Xiang-Phos、Xu-Phos、PC-Phos、TY-Phos、W-Phos及WJ-Phos等多个系列, 具有结构多样、易于修饰、配位位点丰富及立体调控能力优异等特点. 2016年, Sadphos配体首次被应用于不对称丰产金属催化反应, 开启了二者结合的研究新篇章. 系统综述了2016~2026年近十年间, Sadphos配体在丰产金属(铜、镍、钴等)催化的不对称反应及聚合反应中的研究进展, 按丰产金属种类分类, 重点总结其在[3＋2]环加成、不对称加成、不对称交叉偶联、1,1-双取代联烯不对称硼酰基化、还原环化、动态动力学还原共轭加成、轴手性构建、亚磺酰亚胺对映选择性加成/烯基化及联烯单体聚合等反应中的应用, 探讨配体结构与金属中心的匹配性及催化立体调控机制, 分析当前研究面临的挑战, 并对未来发展方向进行展望, 为该领域的进一步研究、结构创新及工业化应用提供参考.

关键词: 不对称催化, 丰产金属催化, 亚磺酰胺膦配体, 聚合反应

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. 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 is systematically summarized. 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 redu- ctive 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.

Key words: asymmetric catalysis, abundant metal catalysis, sulfinamide phosphine ligand, polymerization

引用此文

张瑞楠, 郑琪智, 赖圣怡, 罗文俊, 许冰, 张展鸣, 张俊良. Sadphos在丰产金属催化反应中的应用[J]. 有机化学, 2026, 46(9): 3390-3398.

Ruinan Zhang, Qizhi Zheng, Shengyi Lai, Wenjun Luo, Bing Xu, Zhan-Ming Zhang, Junliang Zhang. Applications of Sadphos in Earth-Abundant Metal Catalysis[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3390-3398.

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图/表 10

图1. 优势手性配体Sadphos家族

Figure 1. Optically active Sadphos ligands

图式1. Cu/Sadphos催化亚甲胺叶立德与β-三氟甲基-β,β-二取代烯酮的不对称[3＋2]环加成反应

Scheme 1. Asymmetric [3＋2] cycloaddition of azomethine ylides with β-trifluoromethyl β,β-disubstituted enones catalyzed by Cu/Sadphos

图式2. Cu/Sadphos催化甲亚胺叶立德与α-三氟甲基-α,β-不饱和酯的不对称[3＋2]环加成反应

Scheme 2. Asymmetric [3＋2] cycloaddition of azomethine ylides with α-trifluoromethyl α,β-unsaturated esters catalyzed by Cu/ Sadphos

图式3. Cu/Sadphos催化不对称[3＋2]环加成反应

Scheme 3. Cu/Sadphos-catalyzed asymmetric [3＋2] cycloaddition reaction

图式4. Cu/Sadphos催化不对称加成反应

Scheme 4. Cu/Sadphos-catalyzed asymmetric addition reaction

图式5. Cu/Sadphos催化双取代联烯的硼酰基化

Scheme 5. Borylation of disubstituted allenes catalyzed by Cu/Sadphos

图式6. Ni/Sadphos在聚合反应中的应用

Scheme 6. Ni/Sadphos in polymerization reactions

图式7. Ni/Sadphos催化的还原环化/交叉偶联反应

Scheme 7. Ni/Sadphos-catalyzed reductive cyclization/cross-coupling reaction

图式8. Ni/Sadphos催化不对称Suzuki-Miyaura轴手性交叉偶联反应

Scheme 8. Asymmetric Suzuki-Miyaura atroposelective cross-coupling reaction catalyzed by Ni/Sadphos

图式9. Co/Sadphos催化的动态动力学还原共轭加成反应

Scheme 9. Co/Sadphos-catalyzed dynamic kinetic reductive conjugate addition reaction

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Sadphos在丰产金属催化反应中的应用

Applications of Sadphos in Earth-Abundant Metal Catalysis

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