2025年47（10）中英文摘要
Ming(鳴)-Phos配體在過渡金屬催化反應中的應用進展
許冰1，張展鳴*2，張俊良*2
(1. 海軍軍醫大學藥學系上海 200433；2. 復旦大學化學系，上海 200438)
摘要：在過渡金屬催化的不對稱反應中，手性配體是實現高對映選擇性的核心因素。其中，手性膦配體作為研究最早且應用最廣泛的手性配體類別，始終受到化學研究者的高度關注。2014年，張俊良課題組基于非C?對稱性、剛柔并濟及兼具軟硬配位原子（O、S、N、P原子）的設計理念，成功開發出首例Sadphos配體――Ming-Phos。該配體憑借結構豐富多樣、易于修飾且可規模化制備等顯著優勢，受到了廣泛關注。截至目前，Ming-Phos配體已應用于金、銀、銅、鈀、銠、鎳6種金屬催化的不對稱反應中，涉及[3+2]環加成、[4+3]環加成、分子內Heck、Heck/Sonogashira、Narasaka-Heck/硅化、Narasaka?Heck/Sonogashira、Larock 吲哚合成、Suzuki偶聯、Sonogashira偶聯、擴環、還原環化/交叉偶聯以及三組分反應等多種反應類型。此外，Ming-Phos配體在丙二烯單體的聚合反應中也展現出優異的區域選擇性和反應活性。經過十年的發展，充分彰顯出該配體在不對稱催化及材料領域的巨大潛力。系統綜述了Ming-Phos配體在過渡金屬催化的不對稱反應及聚合反應中的應用進展，并對其未來發展方向進行了展望。
關鍵詞：不對稱催化；Ming-Phos；金屬催化；聚合反應；亞磺酰胺膦配體
中圖分類號：O62 文獻標識碼：A 文章編號：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-C? 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
銅/多齒陰離子配體催化不對稱自由基反應
陳錚1，董曉陽2，李忠良*2，劉心元*1
（1. 南方科技大學化學系，廣東深圳 518055；2. 大灣區大學物質科學學院，廣東東莞 523000）
摘要：自由基反應在合成化學領域應用非常廣泛，但是自由基高活性的特征使得反應的立體選擇性控制充滿挑戰。圍繞不對稱催化自由基反應這一領域，提出“銅/手性多齒陰離子配體”策略，核心在于設計手性多齒陰離子配體，其不僅能顯著增強銅催化劑的還原性，解決自由基反應啟動的難題，還能夠通過調控銅催化劑的手性環境實現高活性自由基物種的立體選擇性調控。基于該設計思路，首先開發了銅/N,N,P(N)配體催化劑，發展了烷基鹵代烴交叉偶聯、烯烴雙官能化、烷烴碳氫官能化等不對稱催化自由基反應，實現了多種手性化學鍵，如碳-碳、碳-雜、雜-雜鍵的高效構筑。針對純烷基自由基這類挑戰性底物，進一步開發了新型空間限域型配體，通過獨特的手性口袋設計突破立體識別瓶頸，實現了該類自由基的立體選擇性控制，高效構筑手性碳-氮鍵；此外，還設計了Hemilabile型及長邊臂型N,N,N配體，解決了烯基硼酸酯偶聯、大位阻底物反應中的立體選擇性問題。此外，該策略也得到了國內外眾多課題組的驗證。上述“銅/手性多齒陰離子配體”策略的提出與應用，推動了不對稱自由基化學的發展。
關鍵詞：自由基反應；不對稱催化；手性多齒陰離子配體；銅催化；立體選擇性調控
中圖分類號：O62 文獻標識碼：A 文章編號：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
新型錳配合物的合成及其在催化喹啉氫化中的應用
楊浩博，劉強*
（清華大學化學系，北京 100084）
摘要：1,2,3,4-四氫喹啉及其衍生物是重要的有機化合物，廣泛地存在于藥物與生物活性分子骨架之中。以氫氣為氫源的喹啉催化氫化是制備四氫喹啉最直接高效且原子經濟性最高的方法。此外，喹啉也是有應用前景的液態有機儲氫材料。通過催化氫化反應將氫氣轉化為液態的四氫喹啉，易于儲存與運輸。為了實現更溫和條件下的喹啉氫化，在前期工作的基礎上設計并合成了具有高催化活性的新型NNP鉗形錳配合物溴化三羰基·{N-((1H-苯并[d]咪唑-2-基)甲基)-3-(二苯基膦)丙-1-胺}合錳，并通過核磁共振氫譜、核磁共振碳譜、核磁共振磷譜、紅外光譜、高分辨質譜與X射線單晶衍射等手段對其結構進行了詳細地表征。進一步地，在2 mol%上述NNP鉗形錳配合物為催化劑、20 mol%叔丁醇鈉為催化劑活化試劑、0.1 mL四氫呋喃為溶劑、3 MPa氫氣為氫源的條件下，實現了室溫下的喹啉氫化，幾乎定量地得到相應的1,2,3,4-四氫喹啉。對喹啉底物進行拓展，得到11種目標產物，產率均不低于80%，展現出該催化體系具有優異的反應活性與廣泛的底物適用范圍。
關鍵詞：錳配合物；催化；喹啉；氫化；四氫喹啉
中圖分類號：O62 文獻標識碼：A 文章編號：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
手性氮雜環卡賓/金屬催化不對稱羰基加成反應研究進展
阮林新，施世良*
（中國科學院上海有機化學研究所金屬有機化學國家重點實驗室，上海 200032）
摘要：近幾十年來，過渡金屬催化的不對稱反應取得了顯著進展。其中，不對稱羰基加成反應因其能夠高效構建C―C鍵并直接生成手性醇類化合物，受到廣泛關注。手性醇廣泛存在于藥物和天然產物結構中，因此該類反應在有機合成中具有重要價值。手性氮雜環卡賓（NHC）配體憑借其獨特的電子特性和空間結構，在不對稱催化中展現出廣闊的應用潛力。綜述了近年來NHC/金屬催化不對稱羰基加成反應的研究進展，包括酮、醛和亞胺等底物的不對稱芳基化、烯基化和烷基化反應，以及動態動力學不對稱轉化等策略的開發。詳細討論了各類反應的底物適用范圍、應用研究及其反應機理，并結合機理實驗與密度泛函理論（DFT）計算，深入探討了羰基化合物的η2配位活化模式，揭示了手性NHC配體在提升反應活性和實現對映選擇性控制中的關鍵作用。最后，總結了該領域目前面臨的挑戰，如不同類別底物間的反應性差異、對映選擇性與非對映選擇性調控的局限性等，并對未來研究方向進行了展望，以期為新型手性NHC配體的設計及其在不對稱催化中的進一步應用提供參考。
關鍵詞：不對稱催化；金屬催化；手性氮雜環卡賓配體；不對稱羰基加成；手性醇
中圖分類號：O62 文獻標識碼：A 文章編號：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
手性聯咪唑啉的合成及在不對稱自由基偶聯反應中的應用
鐘誠成，陸展*
(浙江大學 化學系 土壤污染防治與安全全國重點實驗室，浙江杭州 310058)
摘要：手性聯咪唑啉（BiIM）配體與手性雙?f唑啉（BOX）體系中的聯?f唑啉（BiOX）存在顯著的結構同源性，其特征在于以氮原子替代氧原子構筑核心骨架。這一結構特征賦予BiIM配體獨特的化學屬性：通過在特定位置引入多樣化取代基，可實現對配位性能的精準電子效應調控，有效調節空間位阻參數與分子剛性，并為非均相催化體系的創新設計提供結構基礎。自2001年Dupont研究團隊首次完成BiIM配體的合成，Casey、宋毛平團隊持續優化合成方法，陸展課題組創新性地以天然α-氨基酸為起始原料，采用模塊化合成策略，成功構建了結構豐富的N-烷基及N-芳基聯咪唑啉配體庫。在不對稱催化領域，陸展團隊率先將BiIM配體應用于不對稱自由基交叉偶聯反應體系，實現了芐位C-H鍵的高效芳基化、烯基化。此后，BilM在自由基反應領域得到了廣泛的關注，無論是在二組分反應還是在三組分反應中都可以適用。盡管當前BiIM配體在實際應用中仍存在體系局限性，且自由基反應固有的選擇性控制等問題亟待解決，但通過配體結構的理性設計優化，并結合計算化學模擬與高通量篩選技術，有望進一步拓展其在藥物合成、復雜分子構建等前沿領域的應用潛力，為現代有機合成化學提供高效的催化策略與技術手段。
關鍵詞：手性聯咪唑啉；配體設計；不對稱催化；交叉偶聯反應；自由基反應
中圖分類號：O62 文獻標識碼：A 文章編號：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
手性二級膦氧在不對稱氫化反應中的研究進展
趙夢龍，韓召斌*
（中國科學院上海有機化學研究所金屬有機化學國家重點實驗室，上海 200032）
摘要：不對稱氫化是制備手性化合物的重要手段，具有高原子經濟性，高效高選擇性及環境友好等優點。反應使用的催化劑通常由過渡金屬和手性三價膦配體組成。由于三價膦單元對空氣和水極度敏感，增加了不對稱氫化的操作難度。二級膦氧（SPO）是一類結構獨特的含磷化合物，其分子結構存在五價磷形態的膦氧和三價磷形態的亞膦酸的互變異構，在自由狀態下以對空氣和水穩定的膦氧結構存在，而與過渡金屬配位時則通常使用配位能力更強的三價磷形態。手性二級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，具有廣泛的結構可調性。二級膦氧與金屬配位后產生的磷-羥基官能團可作為氫鍵的供體協助活化底物。手性二級膦氧的這些特性使其成為一類極具潛力的配體類型。近年來，多類結構多樣的手性二級膦氧被設計合成出來，并應用于過渡金屬催化的碳碳雙鍵、碳氧雙鍵和碳氮雙鍵的不對稱氫化中，取得了優異的催化活性和對映選擇性，部分催化體系已在生物活性分子的高效不對稱合成中發揮作用。根據手性二級膦氧配體的結構進行分類，系統地總結了其作為配體在多種不飽和底物的不對稱氫化中的應用進展和存在的局限，并對后續的發展進行了展望。
關鍵詞：二級膦氧；手性配體；不對稱氫化；互變異構；過渡金屬
中圖分類號：O62 文獻標識碼：A 文章編號：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環鈀催化劑的研究進展
張潤通*1，陳俊1,2，馬保德1，張鳳2，陳根強*3
(1. 深圳職業技術大學碳中和技術研究院，廣東深圳 518055；2. 湖南農業大學 化學與材料科學學院，湖南 長沙 410128；3. 南方科技大學 a.前沿與交叉科學研究院，b.深圳格拉布斯研究院，廣東 深圳 518055)
摘要：環鈀催化劑是一類含有碳鈀鍵的鈀雜環催化劑。由于其結構上的獨特性，在有機合成領域得到了廣泛的應用。Hermann-Beller環鈀催化劑是環鈀催化劑的重要成員，它在Heck反應、Suzuki偶聯反應、Buchwald-Hartwig偶聯反應、碳膦鍵偶聯反應、羰基化反應等多種反應中得到了廣泛的應用，但是目前還缺乏對該類環鈀催化劑的系統介紹與綜述。對Hermann-Beller環鈀催化劑在有機合成中的應用和機理研究進行系統而深入的綜述，并對未來的發展方向進行了展望。
關鍵詞：Hermann-Beller環鈀催化劑；氧化偶聯反應；碳膦鍵偶聯反應；羰基化反應；催化反應機理
中圖分類號：O62 文獻標識碼：A 文章編號：0258-3283（2025）
DOI：10.13822/j.cnki.hxsj.2025.0181
Research Progress on Herrmann?Beller Palladacycle Catalysts ZHANG Run-tong*1, CHEN Jun1,2, 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(許)-Phos配體在過渡金屬催化反應中的應用進展
許冰1，張展鳴*2，張俊良*2
海軍軍醫大學藥學系上海 200433；2. 復旦大學化學系，上海 200438)
摘要：手性膦配體在不對稱催化反應中發揮著核心作用，其膦原子上的取代基類型對反應活性、化學選擇性及立體選擇性具有關鍵影響。富電子二環己基取代的膦結構因優異性能，已在多種手性配體中得到成功應用并展現出高效催化活性。基于此，張俊良課題組將大位阻富電子二環己基膦基團引入自主研發的Sadphos配體骨架，設計合成了一系列含二環己基單膦結構的手性配體Xu-Phos。該類配體具有結構簡潔、易于修飾的特點，且兼具不同軟硬程度的配位原子，可與過渡金屬形成靈活的配位模式，是一類極具應用潛力的手性配體。綜述了近年來以Xu-Phos為優勢手性配體開發的過渡金屬催化不對稱轉化反應研究進展。自2018年首次報道以來，鈀與Xu-Phos形成的催化體系穩定性優異，已成功驅動一系列Heck反應及其相關串聯反應：通過烯烴、炔烴的對映選擇性Heck反應，可高效構建螺手性、中心手性及軸手性化合物；對于芳基碘化物連接的烯烴底物，其對映選擇性Heck反應可通過還原、碳鹵鍵還原消除、Suzuki偶聯、Sonogashira 偶聯、親核鈀化、硼化及遠程碳-氫烷基化等多種路徑終止，從而高化學選擇性、高立體選擇性地合成結構多樣的苯并雜環衍生物。此外，Xu-Phos在鈀催化的烯烴碳胺化、碳醚化、分子內碳氫鍵活化及消除反應中亦表現出優異的不對稱誘導能力，可精準構建多取代雜環化合物及軸向手性環己叉基骨架。除鈀催化體系外，Xu-Phos在其他金屬催化的不對稱反應中也展現出良好應用前景：在銅催化不對稱加成反應中可高效合成手性芳基亞磺酰胺；作為手性單齒膦配體應用于銥催化體系時，能實現酮與仲胺的直接不對稱還原胺化反應。
關鍵詞：不對稱催化；Xu-Phos；鈀催化；亞磺酰胺膦配體；手性化合物
中圖分類號： O62 文獻標識碼：A 文章編號：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-胺基芐基)稀土配合物高效合成工藝研究
余鋼1，沈陽1，趙艷2，陳雄飛*2，袁丹*1，姚英明*1
(1.蘇州大學 材料與化學化工學部，江蘇 蘇州 215006；2.國合通用測試評價認證股份公司，北京 101407)
摘要：報道了三(2-N,N-二甲基胺基芐基)稀土配合物（RER?，RE = Y, La, Sm；R = -o-CH?C?H?NMe?）的合成工藝，通過稀土鹵化物（REX?）與2-N,N-二甲基氨基芐基鉀/鋰鹽的復分解反應，實現了目標配合物的高效制備。采用元素分析、核磁共振氫譜、電感耦合等離子體質譜等分析方法對產物結構和純度進行了表征。深入研究了反應時間、溫度、投料比、重結晶條件等關鍵工藝參數對產物產率的影響規律。結果表明，當投料比控制為n(M-o-CH?C?H?NMe?):n(RECl?) = 2.95:1（M = Li/K）、反應溫度為25 ℃、以THF為溶劑反應2 h時，經甲苯和正己烷的混合溶劑重結晶后，可獲得產率＞90%、單一稀土純度＞99%的目標產物。通過精細化工藝調控，顯著提升了稀土芐基配合物的合成效率與純度，所建立的反應路徑兼具操作便捷性與工業可擴展性，同時為其他稀土配合物的合成工藝開發提供了可借鑒的技術路線和實驗依據，有望進一步推動稀土配合物在高端催化、新能源材料等領域的深度研發和實際應用，為稀土資源的高值化利用提供技術支撐。
關鍵詞：稀土；稀土芐基配合物；工藝優化；產率；純度
中圖分類號：O62 文獻標識碼：A 文章編號：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 (RER?, RE = Y, La, Sm; R =-o-CH?C?H?NMe?). The efficient preparation of the target complexes was achieved through the metathesis reactions between rare earth halides (REX?) 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-CH?C?H?NMe?):n(RECl?) = 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，劉路*
（華東師范大學化學與分子工程學院，上海 200241）
摘要：α-炔基重氮酮作為一種重要的有機合成中間體，由于其既可以用作卡賓前體實現卡賓的反應，又可以發生Wolff重排生成含有炔基的乙烯酮中間體參與后續轉化，近年來正逐漸受到關注。然而，現有的合成方法具有一定的局限性：僅限于使用預先制備的α-炔基酮并通過重氮轉移反應得到對應的α-炔基重氮酮。該方法具有以下缺點：1）綜合產率較低；2）步驟繁瑣需要多次溫度調控；3）反應原料α-炔基酮穩定性差，難以長期保存。因此，開發一種高效便捷的合成方法是必要的。基于此，設計了以α-芳基重氮Weinreb酰胺為關鍵前體的α-炔基重氮酮的合成策略。該策略具有官能團耐受性良好，反應條件溫和，步驟簡便，產率中等至優異等優點。同時，該策略也兼容炔丙基衍生物，為天然產物的衍生提供了平臺。
關鍵詞：α-炔基重氮酮；重氮合成；Weinreb酰胺；α-芳基重氮Weinreb酰胺
中圖分類號：O62 文獻標識碼：A 文章編號：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
具有蝶烯結構的氮雜環卡賓鈀配合物的合成及應用
呂雷陽1，唐嘉偉1，王建軍2，羅偉??/font>2，廖志根3，關麗*1
（1. 中國人民大學 化學與生命資源學院 光轉換材料與生物光子學實驗室，北京 100872；
2. 福建永晶科技股份有限公司 研發部，福建南平 354003）
3.福建省三明市清流縣高級職業中學 化工專業教研室，福建三明 365300）
摘要：氮雜環卡賓是一類具有強σ-供電子能力和立體電子效應可調控的有機配體，在有機催化、過渡金屬催化、光催化合成以及功能材料制備等領域有著廣泛應用。IPrBIDEA-Pd是一種獨特的咪唑型氮雜環卡賓鈀配合物，具有新穎的蝶烯結構。與傳統氮雜環卡賓配合物相比，其咪唑環母體上引入形似蝴蝶翅膀的芳環，在催化過程中發揮著關鍵作用。該設計能有效限制芳胺環繞碳?氮鍵翻轉，抑制β?氫消除反應及催化劑失活現象，從而顯著提升催化劑的周轉數、催化活性和反應選擇性。詳細介紹了IPrBIDEA- Pd的設計、合成及其表征，通過幾個實例對其在有機合成中的應用進行了探討，涵蓋了偕二氟環丙烷的開環還原反應及偶聯反應、2-氟代烯丙基碳酸酯與烯丙基硼酸酯的交叉偶聯反應、雜芳基氯參與的Suzuki-Miyaura反應以及雜芳基二氯參與的Suzuki-Miyaura縮聚反應。期望能夠進一步開發IPrBIDEA配體及其衍生物和金屬配合物在合成化學、催化科學以及功能新材料構建等學科領域的潛在應用價值。
關鍵詞：氮雜環卡賓；鈀配合物；咪唑；有機合成；催化
中圖分類號：O626 文獻標識碼：A 文章編號：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-IPrBIDEA, an imidazolium-type NHC-palladium complex featuring a novel dibenzobarrelene moiety, distinguishes itself. Unlike conventional NHC complexes, IPrBIDEA- 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 IPrBIDEA- 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 IPrBIDEA 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
氧雜蒽骨架手性亞磺酰胺膦配體PC(培超)-Phos
張培超*1，張文文1，趙慶杰1，張俊良*2
(1. 海軍軍醫大學藥學系，上海 200433；2. 復旦大學 化學系，上海 200438)
摘要：不對稱催化是合成手性功能分子最高效的途徑，其中配體的手性傳遞是實現不對稱催化的關鍵。而“理想（IDEAL）”配體的設計開發，一直是合成化學家和工業界共同追求的目標。在近十年來，基于“理想配體”設計理念，電性、骨架和邊臂多樣的新一代動態自適應型手性亞磺酰胺膦配體Sadphos家族被不斷的開發和應用。目前，通過電性調節，改變配體膦原子的電負性和配體空間位阻，Xiang-Phos、Xu-Phos、TY-Phos依次被報道；通過骨架調節，改變配體配位基團的鍵角和配體骨架的剛性，Xiao-Phos、PC-Phos、WJ-Phos、Le-Phos和GF-Phos先后被開發；通過邊臂組裝，引入二苯基甲基膦，開發了一類手性叔丁基亞磺酰胺雙膦配體和多功能有機膦催化劑Wei-Phos。作為基于氧雜蒽骨架最成功的手性配體，目前PC-Phos在不對稱Pictet?Spengler環化、C?S/C?P偶聯、Suzuki偶聯、動力學拆分的去芳構化、鈀雜烯丙基環加成和串聯Heck/Tsuji?Trost等反應時表現出優異的催化活性、化學選擇性和立體選擇性控制能力。聚焦氧雜蒽骨架新型手性亞磺酰胺類單膦配體PC-Phos的設計和應用，系統總結其自2017報道以來在過渡金屬催化的不對稱反應中的研究進展。
關鍵詞：膦配體；手性亞磺酰胺；不對稱催化；氧雜蒽骨架；Sadphos
中圖分類號： O62 文獻標識碼：A 文章編號：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
