Ming(鸣)-Phos配体在过渡金属催化反应中的应用进展

许冰¹，张展鸣^*2，张俊良^*2

(1. 海军军医大学药学系上海 200433；2. 复旦大学化学系，上海  200438) 

摘要：在过渡金属催化的不对称反应中，手性配体是实现高对映选择性的核心因素。其中，手性膦配体作为研究最早且应用最广泛的手性配体类别，始终受到化学研究者的高度关注。2014年，张俊良课题组基于非C₂对称性、刚柔并济及兼具软硬配位原子（O、S、N、P原子）的设计理念，成功开发出首例Sadphos配体――Ming-Phos。该配体凭借结构丰富多样、易于修饰且可规模化制备等显著优势，受到了广泛关注。截至目前，Ming-Phos配体已应用于金、银、铜、钯、铑、镍6种金属催化的不对称反应中，涉及[3+2]环加成、[4+3]环加成、分子内Heck、Heck/Sonogashira、Narasaka-Heck/硅化、Narasaka−Heck/Sonogashira、Larock 吲哚合成、Suzuki偶联、Sonogashira偶联、扩环、还原环化/交叉偶联以及三组分反应等多种反应类型。此外，Ming-Phos配体在丙二烯单体的聚合反应中也展现出优异的区域选择性和反应活性。经过十年的发展，充分彰显出该配体在不对称催化及材料领域的巨大潜力。系统综述了Ming-Phos配体在过渡金属催化的不对称反应及聚合反应中的应用进展，并对其未来发展方向进行了展望。

关键词：不对称催化；Ming-Phos；金属催化；聚合反应；亚磺酰胺膦配体

中图分类号：O62                   文献标识码：A             文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2025.0188

Progress in the Application of Ming-Phos Ligands in Transition-Metal-Catalyzed Reactions Xu Bing¹, Zhang Zhan-ming*², Zhang Jun-liang^*2 (1. School of Pharmacy, Naval Medical University, Shanghai 200433, China; 2.Department of Chemistry, Fudan University, Shanghai 200438, China) 

Abstract：Chiral ligands are the core factor for achieving high enantioselectivity in transition-metal-catalyzed asymmetric reactions. Among them, chiral phosphine ligands, as the earliest studied and most widely applied category of chiral ligands, have always attracted significant attention from chemical researchers. In 2014, the research group of Junliang Zhang successfully developed the first Sadphos ligand, namely Ming-Phos, based on the design concepts of non-C₂ symmetry, a balance between rigidity and flexibility, and the integration of both hard and soft coordinating atoms (O, S, N, and P atoms). Ming-Phos has received extensive attention due to its prominent advantages such as rich structural diversity, ease of modification, and scalability in preparation. To date, Ming-Phos ligands have been employed in asymmetric reactions catalyzed by six metals (gold, silver, copper, palladium, rhodium, and nickel), encompassing diverse reaction types including [3+2] cycloaddition, [4+3] cycloaddition, intramolecular Heck reaction, Heck/Sonogashira reaction, Narasaka-Heck/silylation reaction, Narasaka-Heck/Sonogashira reaction, Larock indole synthesis, Suzuki coupling, Sonogashira coupling, ring expansion, reductive cyclization/cross-coupling, and three-component reaction. Furthermore, Ming-Phos ligands have exhibited superior regioselectivity and reactivity in the polymerization of allene monomers. Over a decade of development, Ming-Phos ligands have fully demonstrated significant potential in the fields of asymmetric catalysis and materials science. This paper systematically reviewed the application progress of Ming-Phos ligands in asymmetric reactions catalyzed by transition metals (including gold, silver, copper, palladium, rhodium, and nickel) as well as in polymerization reactions, and provides an outlook on its future development directions.

Key words：asymmetric catalysis; Ming-Phos; metal catalysis; polymerization reaction; sulfinamide phosphine ligand

铜/多齿阴离子配体催化不对称自由基反应

陈铮¹，董晓阳²，李忠良^*2，刘心元^*1

（1. 南方科技大学化学系，广东深圳  518055；2. 大湾区大学物质科学学院，广东东莞  523000）

摘要：自由基反应在合成化学领域应用非常广泛，但是自由基高活性的特征使得反应的立体选择性控制充满挑战。围绕不对称催化自由基反应这一领域，提出“铜/手性多齿阴离子配体”策略，核心在于设计手性多齿阴离子配体，其不仅能显著增强铜催化剂的还原性，解决自由基反应启动的难题，还能够通过调控铜催化剂的手性环境实现高活性自由基物种的立体选择性调控。基于该设计思路，首先开发了铜/N,N,P(N)配体催化剂，发展了烷基卤代烃交叉偶联、烯烃双官能化、烷烃碳氢官能化等不对称催化自由基反应，实现了多种手性化学键，如碳-碳、碳-杂、杂-杂键的高效构筑。针对纯烷基自由基这类挑战性底物，进一步开发了新型空间限域型配体，通过独特的手性口袋设计突破立体识别瓶颈，实现了该类自由基的立体选择性控制，高效构筑手性碳-氮键；此外，还设计了Hemilabile型及长边臂型N,N,N配体，解决了烯基硼酸酯偶联、大位阻底物反应中的立体选择性问题。此外，该策略也得到了国内外众多课题组的验证。上述“铜/手性多齿阴离子配体”策略的提出与应用，推动了不对称自由基化学的发展。

关键词：自由基反应；不对称催化；手性多齿阴离子配体；铜催化；立体选择性调控

中图分类号：O62     文献标识码：A      文章编号：0258-3283(2025)--

DOI：10.13822/j.cnki.hxsj.2025.0206

Copper/Multidentate Anionic Ligand-Catalyzed Asymmetric Radical Reactions CHEN Zheng¹, DONG Xiao-yang², LI Zhong-liang^*2, LIU Xin-yuan^*1 (1.Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China; 2.School of Physical Sciences, Great Bay University, Dongguan 523000, China)

Abstract: Radical reactions have found broad applications in organic synthesis. However, their high reactivity presents formidable challenges for enantiocontrol. Our team has developed "copper/chiral multidentate anionic ligand" to achieve asymmetric radical transformations. The ligand performs a dual role: it can not only enhance copper's reducing capacity to initiate the radical process but also provide good chrial environment for enantiocontrol over highly reactive radical intermediates. This approach facilitated the development of copper/N,N,P(N)-ligand catalysts, enabling asymmetric transformations, such as enantioconvergent cross-coupling of racemic alkyl halides, alkene difunctionalizations, and C-H functionalizations for efficient construction of chiral C-C, C-heteroatom, and heteroatom?heteroatom bonds. To achieve the enantiocontrol over purely alkyl radicals, we developed spatially confined chiral catalysts. These catalysts feature a chiral pocket characterized by a sterically constrained region around the catalytic center and an expanded spatial cavity at the periphery. Thus, it allows the construction of chiral C-N bond. In addition, we developed hemilabile and long-arm N,N,N-ligands to solve the issues associated with alkenylboronate and sterically encumbered substrates. This strategy has been validated by numerous research groups and provides significantly advances for asymmetric radical chemistry.

Key words: radical reactions; asymmetric catalysis; chiral multidentate anionic ligands; copper catalysts; enantiocontrol

新型锰配合物的合成及其在催化喹啉氢化中的应用

杨浩博，刘强^*

（清华大学化学系，北京  100084）

摘要：1,2,3,4-四氢喹啉及其衍生物是重要的有机化合物，广泛地存在于药物与生物活性分子骨架之中。以氢气为氢源的喹啉催化氢化是制备四氢喹啉最直接高效且原子经济性最高的方法。此外，喹啉也是有应用前景的液态有机储氢材料。通过催化氢化反应将氢气转化为液态的四氢喹啉，易于储存与运输。为了实现更温和条件下的喹啉氢化，在前期工作的基础上设计并合成了具有高催化活性的新型NNP钳形锰配合物溴化三羰基·{N-((1H-苯并[d]咪唑-2-基)甲基)-3-(二苯基膦)丙-1-胺}合锰，并通过核磁共振氢谱、核磁共振碳谱、核磁共振磷谱、红外光谱、高分辨质谱与X射线单晶衍射等手段对其结构进行了详细地表征。进一步地，在2 mol%上述NNP钳形锰配合物为催化剂、20 mol%叔丁醇钠为催化剂活化试剂、0.1 mL四氢呋喃为溶剂、3 MPa氢气为氢源的条件下，实现了室温下的喹啉氢化，几乎定量地得到相应的1,2,3,4-四氢喹啉。对喹啉底物进行拓展，得到11种目标产物，产率均不低于80%，展现出该催化体系具有优异的反应活性与广泛的底物适用范围。

关键词：锰配合物；催化；喹啉；氢化；四氢喹啉

中图分类号：O62      文献标识码：A      文章编号：0258-3283(2025)--

DOI：10.13822/j.cnki.hxsj.2025.0179

Synthesis of A New Manganese Complex and its Application in Catalytic Hydrogenation of Quinolines YANG Hao-bo, LIU Qiang^* (Department of Chemistry, Tsinghua University, Beijing 100084, China)

Abstract: 1,2,3,4-Tetrahydroquinoline and its derivatives are important organic compounds, which are widely present in the frameworks of pharmaceuticals and bioactive molecules. Catalytic hydrogenation of quinolines using hydrogen gas as hydrogen source is the most direct, most effective, and most atom-ecomomical method to obtain tetrahydroquinoline. Furthermore, quinoline is also a promising liquid organic hydrogen storage material. Hydrogen gas can be converted into liquid tetrahydroquinoline through catalytic hydrogenation, which is easy to store and transport. In order to realizing the hydrogenation of quinoline under milder conditions, we designed and synthesised a novel NNP pincer manganese complex [Mn(CO)₃{N-((1H-imidazol-2-yl)methyl-3- (diphenylphosphaneyl)propan-1-amine}]Br with high catalytic activity based on our previous work. The structure of that manganese complex was characterized in detail by ¹HNMR, ¹³CNMR, ³¹PNMR, IR, HRMS and XRD. What’s more, quinoline could be hydrogenated into tetrahydroquinoline almost quantitatively at room temperature catalyzed by 2 mol% that novel NNP pincer manganese complexes with 20 mol% tBuONa as catalyst-activation reagent, tetrahydrofuran as solvent, and 3MPa hydrogen gas as hydrogen source. The quinoline substrates were studied, and eleven target products were obtained with yields of at least 80%. These results showed high activity and broad substrate scope of this catalytic system.

Key words: manganese complex; catalysis; quinoline; hydrogenation; tetrahydroquinoline

手性氮杂环卡宾/金属催化不对称羰基加成反应研究进展

阮林新，施世良^*

（中国科学院上海有机化学研究所金属有机化学国家重点实验室，上海  200032）

摘要：近几十年来，过渡金属催化的不对称反应取得了显著进展。其中，不对称羰基加成反应因其能够高效构建C―C键并直接生成手性醇类化合物，受到广泛关注。手性醇广泛存在于药物和天然产物结构中，因此该类反应在有机合成中具有重要价值。手性氮杂环卡宾（NHC）配体凭借其独特的电子特性和空间结构，在不对称催化中展现出广阔的应用潜力。综述了近年来NHC/金属催化不对称羰基加成反应的研究进展，包括酮、醛和亚胺等底物的不对称芳基化、烯基化和烷基化反应，以及动态动力学不对称转化等策略的开发。详细讨论了各类反应的底物适用范围、应用研究及其反应机理，并结合机理实验与密度泛函理论（DFT）计算，深入探讨了羰基化合物的η²配位活化模式，揭示了手性NHC配体在提升反应活性和实现对映选择性控制中的关键作用。最后，总结了该领域目前面临的挑战，如不同类别底物间的反应性差异、对映选择性与非对映选择性调控的局限性等，并对未来研究方向进行了展望，以期为新型手性NHC配体的设计及其在不对称催化中的进一步应用提供参考。

关键词：不对称催化；金属催化；手性氮杂环卡宾配体；不对称羰基加成；手性醇 

中图分类号：O62       文献标识码：A      文章编号：0258-3283(2025)

DOI：10.13822/j.cnki.hxsj.2025.0183

Progress on Chiral N-Heterocyclic Carbene-Metal Catalyzed Asymmetric Carbonyl Addition Reaction RUAN Lin-xin, SHI Shi-liang^* (State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.) 

Abstract: In recent decades, significant advancements have been achieved in the field of transition metal-catalyzed asymmetric reactions. Among these, asymmetric carbonyl addition reactions have attracted considerable attention due to their efficiency in constructing carbon?carbon bonds and directly producing chiral alcohol compounds. Chiral alcohols are prevalent in drugs and natural products, rendering these reactions highly valuable in organic synthesis. Chiral N-heterocyclic carbene (NHC) ligands, characterized by their distinctive electronic properties and spatial configurations, have shown immense potential in asymmetric catalysis. This article provided a comprehensive review of recent developments in NHC/metal-catalyzed asymmetric carbonyl addition reactions, encompassing the asymmetric arylation, alkenylation, and alkylation of substrates such as ketones, aldehydes, and imines, as well as the exploration of dynamic kinetic asymmetric transformation strategies. The substrate scope, synthetic applications and reaction mechanisms of various transformations were systematically discussed. By integrating mechanistic experiments with density functional theory (DFT) calculations, it explored the η²-coordination activation mode of carbonyl compounds, highlighting the pivotal role of chiral NHC ligands in enhancing reaction efficiency and achieving enantioselective control. In conclusion, the article outlined the current challenges in the field, including reactivity disparities among different substrate classes and limitations in enantioselective and diastereoselective regulation, while also offering perspectives on future research directions. This aims to provide insights for the design of novel chiral NHC ligands and their broader applications in asymmetric catalysis.

Key words: asymmetric catalysis; metal catalysis; chiral N-heterocyclic carbene ligand; asymmetric carbonyl addition; chiral alcohol

手性联咪唑啉的合成及在不对称自由基偶联反应中的应用

钟诚成，陆展^*

(浙江大学 化学系 土壤污染防治与安全全国重点实验室，浙江杭州  310058) 

摘要：手性联咪唑啉（BiIM）配体与手性双?f唑啉（BOX）体系中的联?f唑啉（BiOX）存在显著的结构同源性，其特征在于以氮原子替代氧原子构筑核心骨架。这一结构特征赋予BiIM配体独特的化学属性：通过在特定位置引入多样化取代基，可实现对配位性能的精准电子效应调控，有效调节空间位阻参数与分子刚性，并为非均相催化体系的创新设计提供结构基础。自2001年Dupont研究团队首次完成BiIM配体的合成，Casey、宋毛平团队持续优化合成方法，陆展课题组创新性地以天然α-氨基酸为起始原料，采用模块化合成策略，成功构建了结构丰富的N-烷基及N-芳基联咪唑啉配体库。在不对称催化领域，陆展团队率先将BiIM配体应用于不对称自由基交叉偶联反应体系，实现了苄位C-H键的高效芳基化、烯基化。此后，BilM在自由基反应领域得到了广泛的关注，无论是在二组分反应还是在三组分反应中都可以适用。尽管当前BiIM配体在实际应用中仍存在体系局限性，且自由基反应固有的选择性控制等问题亟待解决，但通过配体结构的理性设计优化，并结合计算化学模拟与高通量筛选技术，有望进一步拓展其在药物合成、复杂分子构建等前沿领域的应用潜力，为现代有机合成化学提供高效的催化策略与技术手段。

关键词：手性联咪唑啉；配体设计；不对称催化；交叉偶联反应；自由基反应 

中图分类号：O62             文献标识码：A               文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2025.0203

Synthesis and Application of Chiral Biimidazolines in Asymmetric Radical Couplings ZHONG Cheng-cheng, LU Zhan^* (State Key Laboratory of Soil Pollution Control and safety, Department of Chemistry, Zhejiang University, Hangzhou 310058, China)

Abstract：The chiral bipyrimidinol (BiIM) ligand and the chiral bisoxazoline (BOX) system exhibit significant structural homology, characterized by the substitution of nitrogen atoms for oxygen atoms to construct the core framework. This structural feature endows the BiIM ligand with unique chemical properties: by introducing diverse substituents at specific positions, precise electronic effects on coordination performance can be achieved, effectively regulating steric parameters and molecular rigidity, and providing a structural foundation for innovative design in heterogeneous catalytic systems. Since the first synthesis of the BiIM ligand by the Dupont research team in 2001, the Casey and Song Maoping teams have continuously optimized the synthetic methods. The Lu Zhan group innovatively used natural α-amino acids as starting materials and adopted a modular synthesis strategy to successfully construct a structurally rich library of N-alkyl and N-aryl bipyrimidinol ligands. In asymmetric catalysis, the Lu Zhan team was the first to apply the BiIM ligand to asymmetric radical cross-coupling reaction systems, achieving efficient arylation and alkenylation of benzylic C-H bonds. Subsequently, BilM has received extensive attention in radical reactions, applicable in both two-component and three-component reactions. Despite current limitations in practical applications of BiIM ligands and inherent selectivity control issues in radical reactions, rational design optimization of ligand structures combined with computational chemistry simulations and high-throughput screening techniques may further expand their application potential in drug synthesis and complex molecule construction, providing efficient catalytic strategies and technological means for modern organic synthesis chemistry.

Key words: chiral biimidazoline; ligand design; asymmetric catalysis; cross-coupling reaction; radical reaction

手性二级膦氧在不对称氢化反应中的研究进展

赵梦龙，韩召斌^*

（中国科学院上海有机化学研究所金属有机化学国家重点实验室，上海  200032）

摘要：不对称氢化是制备手性化合物的重要手段，具有高原子经济性，高效高选择性及环境友好等优点。反应使用的催化剂通常由过渡金属和手性三价膦配体组成。由于三价膦单元对空气和水极度敏感，增加了不对称氢化的操作难度。二级膦氧（SPO）是一类结构独特的含磷化合物，其分子结构存在五价磷形态的膦氧和三价磷形态的亚膦酸的互变异构，在自由状态下以对空气和水稳定的膦氧结构存在，而与过渡金属配位时则通常使用配位能力更强的三价磷形态。手性二级膦氧化合物的手性中心可位于磷原子上、磷的取代基上，或者二者兼具手性，具有广泛的结构可调性。二级膦氧与金属配位后产生的磷-羟基官能团可作为氢键的供体协助活化底物。手性二级膦氧的这些特性使其成为一类极具潜力的配体类型。近年来，多类结构多样的手性二级膦氧被设计合成出来，并应用于过渡金属催化的碳碳双键、碳氧双键和碳氮双键的不对称氢化中，取得了优异的催化活性和对映选择性，部分催化体系已在生物活性分子的高效不对称合成中发挥作用。根据手性二级膦氧配体的结构进行分类，系统地总结了其作为配体在多种不饱和底物的不对称氢化中的应用进展和存在的局限，并对后续的发展进行了展望。

关键词：二级膦氧；手性配体；不对称氢化；互变异构；过渡金属

中图分类号：O62                       文献标识码：A             文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2025.0178

Research Progress of Chiral Secondary Phosphine Oxides in Asymmetric Hydrogenation Reactions ZHAO Meng-long, HAN Zhao-bin^*( State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China) 

Abstract：Asymmetric hydrogenation is an important method for the preparation of chiral compounds, featuring advantages such as high atom economy, high efficiency, high selectivity, and environmental friendliness. The catalysts used are typically composed of transition metals and chiral trivalent phosphine ligands. However, trivalent phosphine moieties are normally sensitive to air and moisture, which increases the operational difficulty of asymmetric hydrogenation. Secondary phosphine oxides (SPOs), a unique class of phosphorus-containing compounds, exhibit a tautomeric equilibrium between the phosphine oxide (pentavalent phosphorus form) and the phosphinous acid (trivalent phosphorus form). SPOs normally exist in the phosphine oxide form in the free state, which is inert to air and moisture. While in coordination with transition metals, they preferentially adopt the trivalent phosphorus form with stronger coordination ability. The chiral elements of chiral secondary phosphine oxides can be located on the phosphorus atom, in the substituents of phosphorus, or both, offering extensive structural tunability. The phosphorus-hydroxyl (P-OH) functional group generated after the coordination of secondary phosphine oxide with transition metal can act as hydrogen bond donors to assist in in substrate activation. These characteristics make chiral secondary phosphine oxides a highly promising class of ligands. In recent years, numerous structurally diverse chiral SPOs have been designed, synthesized, and successfully applied in transition metal catalyzed asymmetric hydrogenation of unsaturated double bonds including C=C bonds, C=O bonds, and C=N bonds. These catalysts have demonstrated excellent activity and enantioselectivity, wherein several catalytic systems have proven effective in the efficient synthesis of bioactive molecules. Based on the structural classification of chiral secondary phosphine oxide ligands, the advances and challenges in using SPOs as chiral ligands in transition metalcatalyzed asymmetric hydrogenation of diverse unsaturated substrates were summarized,  and the prospects of future developments in this field are also discussed.

Key words：secondary phosphine oxide; chiral ligand; asymmetric hydrogenation; tautomerism; transition metal

Hermann-Beller环钯催化剂的研究进展

张润通^*1，陈俊^1,2，马保德¹，张凤²，陈根强^*3

(1. 深圳职业技术大学碳中和技术研究院，广东深圳  518055；2. 湖南农业大学 化学与材料科学学院，湖南 长沙  410128；3. 南方科技大学 a.前沿与交叉科学研究院，b.深圳格拉布斯研究院，广东 深圳  518055)

摘要：环钯催化剂是一类含有碳钯键的钯杂环催化剂。由于其结构上的独特性，在有机合成领域得到了广泛的应用。Hermann-Beller环钯催化剂是环钯催化剂的重要成员，它在Heck反应、Suzuki偶联反应、Buchwald-Hartwig偶联反应、碳膦键偶联反应、羰基化反应等多种反应中得到了广泛的应用，但是目前还缺乏对该类环钯催化剂的系统介绍与综述。对Hermann-Beller环钯催化剂在有机合成中的应用和机理研究进行系统而深入的综述，并对未来的发展方向进行了展望。

关键词：Hermann-Beller环钯催化剂；氧化偶联反应；碳膦键偶联反应；羰基化反应；催化反应机理

中图分类号：O62            文献标识码：A             文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2025.0181

Research Progress on Herrmann?Beller Palladacycle Catalysts ZHANG Run-tong^*1, CHEN Jun^1,2, MA Bao-de¹, ZHANG Feng²,CHEN Gen-qiang^*3 (1. Institute of Carbon Neutral Technology, Shenzhen Polytechnic University, Shenzhen 518055,China; 2. College of Chemistry and Materials Science, Hunan Agricultural University, Changsha 410128,China; 3a. Academy for Advanced Interdisciplinary Studies, 3b. Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen 518055,China)

Abstract：Palladacyclic catalysts are a class of palladium heterocycles featuring Pd?C bonds, whose unique structures have led to widespread applications in organic synthesis. Among them, the Hermann?Beller palladacycle stands out as a particularly versatile catalyst, having been employed in Heck reactions, Suzuki?Miyaura couplings, Buchwald?Hartwig aminations, C?P bond forming processes, carbonylations, and more. Despite its prominence, no systematic reviewed of this catalyst class currently exists. Here, we present a comprehensive and in‑depth survey of the Hermann?Beller palladacycle’s applications and mechanistic insights in organic synthesis, and we conclude with an outlook on emerging trends and future research directions.

Key words：Hermann?Beller palladacycle catalyst; oxidative coupling reaction; C―P bond coupling reaction; carbonylation reaction; catalytic reaction mechanism

Xu(许)-Phos配体在过渡金属催化反应中的应用进展

许冰¹，张展鸣^*2，张俊良^*2

海军军医大学药学系上海 200433；2. 复旦大学化学系，上海  200438) 

摘要：手性膦配体在不对称催化反应中发挥着核心作用，其膦原子上的取代基类型对反应活性、化学选择性及立体选择性具有关键影响。富电子二环己基取代的膦结构因优异性能，已在多种手性配体中得到成功应用并展现出高效催化活性。基于此，张俊良课题组将大位阻富电子二环己基膦基团引入自主研发的Sadphos配体骨架，设计合成了一系列含二环己基单膦结构的手性配体Xu-Phos。该类配体具有结构简洁、易于修饰的特点，且兼具不同软硬程度的配位原子，可与过渡金属形成灵活的配位模式，是一类极具应用潜力的手性配体。综述了近年来以Xu-Phos为优势手性配体开发的过渡金属催化不对称转化反应研究进展。自2018年首次报道以来，钯与Xu-Phos形成的催化体系稳定性优异，已成功驱动一系列Heck反应及其相关串联反应：通过烯烃、炔烃的对映选择性Heck反应，可高效构建螺手性、中心手性及轴手性化合物；对于芳基碘化物连接的烯烃底物，其对映选择性Heck反应可通过还原、碳卤键还原消除、Suzuki偶联、Sonogashira 偶联、亲核钯化、硼化及远程碳-氢烷基化等多种路径终止，从而高化学选择性、高立体选择性地合成结构多样的苯并杂环衍生物。此外，Xu-Phos在钯催化的烯烃碳胺化、碳醚化、分子内碳氢键活化及消除反应中亦表现出优异的不对称诱导能力，可精准构建多取代杂环化合物及轴向手性环己叉基骨架。除钯催化体系外，Xu-Phos在其他金属催化的不对称反应中也展现出良好应用前景：在铜催化不对称加成反应中可高效合成手性芳基亚磺酰胺；作为手性单齿膦配体应用于铱催化体系时，能实现酮与仲胺的直接不对称还原胺化反应。

关键词：不对称催化；Xu-Phos；钯催化；亚磺酰胺膦配体；手性化合物

中图分类号： O62         文献标识码：A             文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2025.0189

Progress in the Application of Xu-Phos Ligands in Transition-Metal-Catalyzed Asymmetric Reactions Xu Bing¹, Zhang Zhan-ming^*2, Zhang Jun-liang^*2 (1. School of Pharmacy, Naval Medical University, Shanghai 200433, China; 2.Department of Chemistry, Fudan University, Shanghai 200438, China) 

Abstract：Chiral phosphine ligands play a central role in asymmetric catalytic reactions, and the types of substituents on their phosphorus atoms have a critical impact on reaction activity, chemo- and stereoselectivity. Phosphine structures with electron-rich dicyclohexyl substituents have been successfully applied in various chiral ligands and demonstrated high catalytic activity due to their excellent performance. Based on this, the research group of Junliang Zhang introduced the sterically hindered and electron-rich dicyclohexylphosphine group into the self-developed Sadphos ligand framework, designing and synthesizing a series of chiral ligands named Xu-Phos that contain a dicyclohexyl monophosphine structure. These ligands feature a simple structure, easy modification, and possess coordination atoms with different hardness and softness, enabling flexible coordination with transition metals, thus emerging as a class of chiral ligands with great application potential. This paper reviewed the research progress in the development of transition-metal-catalyzed asymmetric transformation reactions using Xu-Phos as a privileged chiral ligand in recent years. Since its first report in 2018, the catalytic system formed by palladium and Xu-Phos has exhibited excellent stability and successfully driven a series of Heck reactions and their related tandem reactions: Enantioselective Heck reactions of alkenes and alkynes allow for the efficient construction of spirochiral, central chiral, and axially chiral compounds; For alkene substrates linked to aryl iodides, their enantioselective Heck reactions can be terminated through multiple pathways such as reduction, reductive elimination of carbon-halogen bonds, Suzuki coupling, Sonogashira coupling, nucleophilic palladation, borylation, and remote C-H alkylation, thereby generating structurally diverse benzheterocyclic derivatives with high chemo- and stereoselectivity. In addition, Xu-Phos also shows excellent asymmetric induction ability in palladium-catalyzed alkene carboamination, carboetherification, intramolecular C-H bond activation, and elimination reactions, enabling the precise construction of various substituted heterocyclic compounds and axially chiral cyclohexylidene skeletons. Beyond its outstanding performance in palladium-catalyzed asymmetric reactions, Xu-Phos has also shown promise in other metal-catalyzed reactions. It can efficiently synthesize chiral aryl sulfinamides through copper-catalyzed asymmetric addition reactions. When applied as a chiral monodentate phosphine ligand in iridium-catalyzed systems, Xu-Phos enables the direct asymmetric reductive amination of ketones with secondary amines.

Key words：asymmetric catalysis; Xu-Phos; palladium-catalyzed; sulfinamide phosphine ligand; chiral compound

三(2-胺基苄基)稀土配合物高效合成工艺研究

余钢¹，沈阳¹，赵艳²，陈雄飞^*2，袁丹^*1，姚英明^*1

(1.苏州大学 材料与化学化工学部，江苏 苏州  215006；2.国合通用测试评价认证股份公司，北京  101407)

摘要：报道了三(2-N,N-二甲基胺基苄基)稀土配合物（RER₃，RE = Y, La, Sm；R = -o-CH₂C₆H₄NMe₂）的合成工艺，通过稀土卤化物（REX₃）与2-N,N-二甲基氨基苄基钾/锂盐的复分解反应，实现了目标配合物的高效制备。采用元素分析、核磁共振氢谱、电感耦合等离子体质谱等分析方法对产物结构和纯度进行了表征。深入研究了反应时间、温度、投料比、重结晶条件等关键工艺参数对产物产率的影响规律。结果表明，当投料比控制为n(M-o-CH₂C₆H₄NMe₂):n(RECl₃) = 2.95:1（M = Li/K）、反应温度为25 ℃、以THF为溶剂反应2 h时，经甲苯和正己烷的混合溶剂重结晶后，可获得产率＞90%、单一稀土纯度＞99%的目标产物。通过精细化工艺调控，显著提升了稀土苄基配合物的合成效率与纯度，所建立的反应路径兼具操作便捷性与工业可扩展性，同时为其他稀土配合物的合成工艺开发提供了可借鉴的技术路线和实验依据，有望进一步推动稀土配合物在高端催化、新能源材料等领域的深度研发和实际应用，为稀土资源的高值化利用提供技术支撑。

关键词：稀土；稀土苄基配合物；工艺优化；产率；纯度

中图分类号：O62              文献标识码：A                  文章编号：0258-3283（2025）--

DOI：10.13822/j.cnki.hxsj.2025.0208

Study on the Efficient Synthetic Process of Tris(2-Aminobenzyl) Rare Earth Complexes YU Gang¹, SHEN Yang¹, ZHAO Yan², CHEN Xiong-fei^*2, YUAN Dan^*1, YAO Ying-ming^*1 (1.College of Materials, Chemistry and Chemical Engineering, Soochow University, Suzhou 215006, China;2.China United Test & Certification Co., Ltd., Beijing 101407, China)

Abstract：This paper reported the synthetic process of tris(2-N,N-dimethylaminobenzyl) rare earth complexes (RER₃, RE = Y, La, Sm; R =-o-CH₂C₆H₄NMe₂). The efficient preparation of the target complexes was achieved through the metathesis reactions between rare earth halides (REX₃) and 2-N,N-dimethylamino benzyl lithium/potassium salts. The products were characterized by elemental analysis (EA), ¹H NMR spectroscopy, ICP-MS. This study systematically explored the influence of key parameters, such as reaction time, temperature, feed ratio, recrystallization conditions, on the product yield and purity. The optimal conditions were as follows: the feed ratio controlled at n(M-o-CH₂C₆H₄NMe₂):n(RECl₃) = 2.95:1 (M=Li/K), reaction temperature at 25 ℃ in THF for 2 hours, and recrystallization in the mixture of toluene and n-hexane. The target products were obtained in >90% yields and >99% purity for rare earth. Through refined process control, this study has significantly improved the synthesis efficiency and purity of rare earth benzyl complexes. The established reaction route features both operational convenience and industrial scalability, while providing a reference technical route and experimental basis for the development of synthesis processes for other rare earth complexes. It is expected to further promote the in-depth research, development and practical application of rare earth complexes in fields such as high-end catalysis and new energy materials, and offer technical support for the high-value utilization of rare earth resources.

Keywords：rare earth; rare earth benzyl complexes; process optimization; yield; purity

α-炔基重氮酮的高效合成研究

徐田媛，倪宇豪，刘路^*

（华东师范大学化学与分子工程学院，上海  200241）

摘要：α-炔基重氮酮作为一种重要的有机合成中间体，由于其既可以用作卡宾前体实现卡宾的反应，又可以发生Wolff重排生成含有炔基的乙烯酮中间体参与后续转化，近年来正逐渐受到关注。然而，现有的合成方法具有一定的局限性：仅限于使用预先制备的α-炔基酮并通过重氮转移反应得到对应的α-炔基重氮酮。该方法具有以下缺点：1）综合产率较低；2）步骤繁琐需要多次温度调控；3）反应原料α-炔基酮稳定性差，难以长期保存。因此，开发一种高效便捷的合成方法是必要的。基于此，设计了以α-芳基重氮Weinreb酰胺为关键前体的α-炔基重氮酮的合成策略。该策略具有官能团耐受性良好，反应条件温和，步骤简便，产率中等至优异等优点。同时，该策略也兼容炔丙基衍生物，为天然产物的衍生提供了平台。

关键词：α-炔基重氮酮；重氮合成；Weinreb酰胺；α-芳基重氮Weinreb酰胺

中图分类号：O62         文献标识码：A             文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2025.0187

Efficient Synthesis of α-Alkynyl Diazo Ketones  XU Tian-yuan, NI Yu-hao, LIU Lu^* (School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241, China) 

Abstract：α-Alkynyl diazo ketones, as important intermediates in organic synthesis, have garnered increasing attention in recent years due to their dual reactivity: they can serve as carbene precursors to undergo carbene-involved reactions or undergo Wolff rearrangement to generate alkynyl-containing ketene intermediates for subsequent transformations. However, existing synthetic methods exhibit certain limitations, being restricted to the use of pre-prepared α-alkynyl ketones followed by diazo transfer reactions to yield the corresponding α-alkynyl diazo ketones. This approach suffers from several drawbacks: 1) low overall yields; 2) tedious procedures requiring multiple temperature adjustments; 3) poor stability of the starting α-alkynyl ketones, which are difficult to store long-term. Therefore, the development of an efficient and convenient synthetic method is imperative. To address this, a novel strategy for synthesizing α-alkynyl diazo ketones has been designed, employing α-aryl diazo Weinreb amides as key precursors. This strategy offers several advantages, including excellent functional group tolerance, mild reaction conditions, straightforward procedures, and moderate to excellent yields. Additionally, this approach is compatible with propargyl derivatives, providing a versatile platform for the derivatization of natural products.

Key words：α-alkynyl diazo ketones; diazo synthesis; Weinreb amide; α-aryl diazo Weinreb amide 

具有蝶烯结构的氮杂环卡宾钯配合物的合成及应用

吕雷阳¹，唐嘉伟¹，王建军²，罗伟??/font>²，廖志根³，关丽^*1

（1. 中国人民大学 化学与生命资源学院 光转换材料与生物光子学实验室，北京 100872；

2. 福建永晶科技股份有限公司 研发部，福建南平 354003）

3.福建省三明市清流县高级职业中学 化工专业教研室，福建三明 365300）

摘要：氮杂环卡宾是一类具有强σ-供电子能力和立体电子效应可调控的有机配体，在有机催化、过渡金属催化、光催化合成以及功能材料制备等领域有着广泛应用。IPr^BIDEA-Pd是一种独特的咪唑型氮杂环卡宾钯配合物，具有新颖的蝶烯结构。与传统氮杂环卡宾配合物相比，其咪唑环母体上引入形似蝴蝶翅膀的芳环，在催化过程中发挥着关键作用。该设计能有效限制芳胺环绕碳−氮键翻转，抑制β−氢消除反应及催化剂失活现象，从而显著提升催化剂的周转数、催化活性和反应选择性。详细介绍了IPr^BIDEA- Pd的设计、合成及其表征，通过几个实例对其在有机合成中的应用进行了探讨，涵盖了偕二氟环丙烷的开环还原反应及偶联反应、2-氟代烯丙基碳酸酯与烯丙基硼酸酯的交叉偶联反应、杂芳基氯参与的Suzuki-Miyaura反应以及杂芳基二氯参与的Suzuki-Miyaura缩聚反应。期望能够进一步开发IPr^BIDEA配体及其衍生物和金属配合物在合成化学、催化科学以及功能新材料构建等学科领域的潜在应用价值。

关键词：氮杂环卡宾；钯配合物；咪唑；有机合成；催化

中图分类号：O626              文献标识码：A              文章编号：0258-3283（2025）--

DOI: 10.13822/j.cnki.hxsj.2025.0153

Dibenzobarrelene-Functionalized N-Heterocyclic Carbene Palladium Complexes: Synthesis and Catalytic Applications LV Lei-yang¹, TANG Jia-Wei¹, WANG Jian-jun², LUO Wei-fen², LIAO Zhi-gen³, GUAN Li^*1（1. Key Laboratory of Advanced Light Conversion Materials and Biophotonics, School of Chemistry and Life Resources, Renmin University of China, Beijing 100872, China; 2.Center of Research and Development, Fujian Yongjing Technology Co., Ltd., Nanping 354003, China; 3. Department of Chemical Engineering, Qingliu Senior Vocational High School, Sanming 365300, China）

Abstract：N-heterocyclic carbenes (NHCs), known for their strong σ-donating properties and tunable stereo-electronic effects, have found extensive applications in organic catalysis, transition metal catalysis, photocatalytic synthesis, and the preparation of functional materials. Among them, Pd-IPr^BIDEA, an imidazolium-type NHC-palladium complex featuring a novel dibenzobarrelene moiety, distinguishes itself. Unlike conventional NHC complexes, IPr^BIDEA- Pd incorporates butterfly-wing-like aromatic rings into its imidazolium core, playing a pivotal role in catalytic processes. This innovative design effectively restricts the flipping of aromatic amines around the C−N bond, thereby suppressing β−H elimination and catalyst deactivation. As a result, it significantly enhances the catalyst's turnover frequency, activity, and the selectivity of reactions. This review provided a comprehensive introduction to the design, synthesis, and characterization of IPr^BIDEA- Pd complex, accompanied by a detailed discussion of its application in organic synthesis, including the ring-opening reduction and coupling reaction of gem-difluorocyclopropanes, the cross-coupling reaction of 2-fluoroallyl carbonates with allyl boronates, the Suzuki-Miyaura reaction involving heteroaryl chlorides, and the Suzuki-Miyaura polycondensation involving heteroaryl dichlorides. Consequently, it is anticipated that the potential applications of IPr^BIDEA ligand and its derivatives and metal complexes in the domains of synthetic chemistry, catalytic science, and the development of new functional materials can be further advanced.

Key words：N-heterocyclic carbene; palladium complex; imidazole; organic synthesis; catalysis

氧杂蒽骨架手性亚磺酰胺膦配体PC(培超)-Phos

张培超^*1，张文文¹，赵庆杰¹，张俊良^*2

(1. 海军军医大学药学系，上海  200433；2. 复旦大学 化学系，上海  200438) 

摘要：不对称催化是合成手性功能分子最高效的途径，其中配体的手性传递是实现不对称催化的关键。而“理想（IDEAL）”配体的设计开发，一直是合成化学家和工业界共同追求的目标。在近十年来，基于“理想配体”设计理念，电性、骨架和边臂多样的新一代动态自适应型手性亚磺酰胺膦配体Sadphos家族被不断的开发和应用。目前，通过电性调节，改变配体膦原子的电负性和配体空间位阻，Xiang-Phos、Xu-Phos、TY-Phos依次被报道；通过骨架调节，改变配体配位基团的键角和配体骨架的刚性，Xiao-Phos、PC-Phos、WJ-Phos、Le-Phos和GF-Phos先后被开发；通过边臂组装，引入二苯基甲基膦，开发了一类手性叔丁基亚磺酰胺双膦配体和多功能有机膦催化剂Wei-Phos。作为基于氧杂蒽骨架最成功的手性配体，目前PC-Phos在不对称Pictet?Spengler环化、C?S/C?P偶联、Suzuki偶联、动力学拆分的去芳构化、钯杂烯丙基环加成和串联Heck/Tsuji−Trost等反应时表现出优异的催化活性、化学选择性和立体选择性控制能力。聚焦氧杂蒽骨架新型手性亚磺酰胺类单膦配体PC-Phos的设计和应用，系统总结其自2017报道以来在过渡金属催化的不对称反应中的研究进展。

关键词：膦配体；手性亚磺酰胺；不对称催化；氧杂蒽骨架；Sadphos

中图分类号： O62          文献标识码：A             文章编号：0258-3283（2025）

DOI：10.13822/j.cnki.hxsj.2025.0218

PC-Phos: A Xanthene-Derived Chiral Sulfinamide-Phosphine Ligand Zhang Pei-Chao^*1, Zhang Wen-wen¹, Zhao Qing-jie¹, Zhang Jun-liang*²(1.School of Pharmacy, Naval Medical University, Shanghai 200433, China; 2.Department of Chemistry, Fudan University, Shanghai 200438, China) 

Abstract：Asymmetric catalysis is the most efficient approach for the synthesis of chiral functional molecules, among which the chiral transfer of ligands is the key to achieving asymmetric catalysis. The design and development of "IDEAL" ligands have always been the common goal pursued by synthetic chemists and the industry. In the past decade, based on the design concept of "ideal ligands", a new generation of dynamically adaptive chiral sulfinamide phosphine ligands of the Sadphos family with diverse electrical properties, skeletons and side arms have been continuously developed and applied. Currently, electronic tuning strategies―modulating the phosphorus atom’s electronegativity and the steric hindrance of the ligands―have led to the successive development of Xiang-Phos, Xu-Phos, and TY-Phos. Skeletal tuning, involving adjustment of coordination group bond angles and backbone rigidity, has afforded Xiao-Phos, PC-Phos, WJ-Phos, Le-Phos, and GF-Phos. Moreover, side-arm assembly through incorporation of diphenylmethylphosphine has enabled the design of a class of chiral tert-butanesulfinamide-based bisphosphine ligands, as well as the multifunctional organophosphorus catalyst Wei-Phos. As one of the most successful chiral ligands based on a xanthene scaffold, PC-Phos has demonstrated excellent catalytic activity, chemoselectivity, and stereoselectivity control in various asymmetric transformations, including Pictet?Spengler cyclization, C?S/C?P coupling, Suzuki coupling, kinetic resolution via dearomatization, palladium-heteroallyl cycloaddition, and tandem Heck/Tsuji?Trost reactions. This review focuses on the design and application of PC-Phos, a new type of Sadphos with the xanthene skeleton, and systematically summarizes its research progress in transition metal-catalyzed asymmetric reactions from 2017 to 2025.

Key words：phosphine ligands; chiral sulfinamide; asymmetric catalysis;xanthene; Sadphos