2025年47（10）中英文摘要
Ming(鳴)-Phos配體在過渡金屬催化反應(yīng)中的應(yīng)用進(jìn)展
許冰1，張展鳴*2，張俊良*2
(1. 海軍軍醫(yī)大學(xué)藥學(xué)系上海 200433；2. 復(fù)旦大學(xué)化學(xué)系，上海 200438)
摘要：在過渡金屬催化的不對(duì)稱反應(yīng)中，手性配體是實(shí)現(xiàn)高對(duì)映選擇性的核心因素。其中，手性膦配體作為研究最早且應(yīng)用最廣泛的手性配體類別，始終受到化學(xué)研究者的高度關(guān)注。2014年，張俊良課題組基于非C?對(duì)稱性、剛?cè)岵?jì)及兼具軟硬配位原子（O、S、N、P原子）的設(shè)計(jì)理念，成功開發(fā)出首例Sadphos配體――Ming-Phos。該配體憑借結(jié)構(gòu)豐富多樣、易于修飾且可規(guī)模化制備等顯著優(yōu)勢(shì)，受到了廣泛關(guān)注。截至目前，Ming-Phos配體已應(yīng)用于金、銀、銅、鈀、銠、鎳6種金屬催化的不對(duì)稱反應(yīng)中，涉及[3+2]環(huán)加成、[4+3]環(huán)加成、分子內(nèi)Heck、Heck/Sonogashira、Narasaka-Heck/硅化、Narasaka?Heck/Sonogashira、Larock 吲哚合成、Suzuki偶聯(lián)、Sonogashira偶聯(lián)、擴(kuò)環(huán)、還原環(huán)化/交叉偶聯(lián)以及三組分反應(yīng)等多種反應(yīng)類型。此外，Ming-Phos配體在丙二烯單體的聚合反應(yīng)中也展現(xiàn)出優(yōu)異的區(qū)域選擇性和反應(yīng)活性。經(jīng)過十年的發(fā)展，充分彰顯出該配體在不對(duì)稱催化及材料領(lǐng)域的巨大潛力。系統(tǒng)綜述了Ming-Phos配體在過渡金屬催化的不對(duì)稱反應(yīng)及聚合反應(yīng)中的應(yīng)用進(jìn)展，并對(duì)其未來發(fā)展方向進(jìn)行了展望。
關(guān)鍵詞：不對(duì)稱催化；Ming-Phos；金屬催化；聚合反應(yīng)；亞磺酰胺膦配體
中圖分類號(hào)：O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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(duì)稱自由基反應(yīng)
陳錚1，董曉陽2，李忠良*2，劉心元*1
（1. 南方科技大學(xué)化學(xué)系，廣東深圳 518055；2. 大灣區(qū)大學(xué)物質(zhì)科學(xué)學(xué)院，廣東東莞 523000）
摘要：自由基反應(yīng)在合成化學(xué)領(lǐng)域應(yīng)用非常廣泛，但是自由基高活性的特征使得反應(yīng)的立體選擇性控制充滿挑戰(zhàn)。圍繞不對(duì)稱催化自由基反應(yīng)這一領(lǐng)域，提出“銅/手性多齒陰離子配體”策略，核心在于設(shè)計(jì)手性多齒陰離子配體，其不僅能顯著增強(qiáng)銅催化劑的還原性，解決自由基反應(yīng)啟動(dòng)的難題，還能夠通過調(diào)控銅催化劑的手性環(huán)境實(shí)現(xiàn)高活性自由基物種的立體選擇性調(diào)控。基于該設(shè)計(jì)思路，首先開發(fā)了銅/N,N,P(N)配體催化劑，發(fā)展了烷基鹵代烴交叉偶聯(lián)、烯烴雙官能化、烷烴碳?xì)涔倌芑炔粚?duì)稱催化自由基反應(yīng)，實(shí)現(xiàn)了多種手性化學(xué)鍵，如碳-碳、碳-雜、雜-雜鍵的高效構(gòu)筑。針對(duì)純烷基自由基這類挑戰(zhàn)性底物，進(jìn)一步開發(fā)了新型空間限域型配體，通過獨(dú)特的手性口袋設(shè)計(jì)突破立體識(shí)別瓶頸，實(shí)現(xiàn)了該類自由基的立體選擇性控制，高效構(gòu)筑手性碳-氮鍵；此外，還設(shè)計(jì)了Hemilabile型及長邊臂型N,N,N配體，解決了烯基硼酸酯偶聯(lián)、大位阻底物反應(yīng)中的立體選擇性問題。此外，該策略也得到了國內(nèi)外眾多課題組的驗(yàn)證。上述“銅/手性多齒陰離子配體”策略的提出與應(yīng)用，推動(dòng)了不對(duì)稱自由基化學(xué)的發(fā)展。
關(guān)鍵詞：自由基反應(yīng)；不對(duì)稱催化；手性多齒陰離子配體；銅催化；立體選擇性調(diào)控
中圖分類號(hào)：O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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(yīng)用
楊浩博，劉強(qiáng)*
（清華大學(xué)化學(xué)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(jī)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(jīng)濟(jì)性最高的方法。此外，喹啉也是有應(yīng)用前景的液態(tài)有機(jī)儲(chǔ)氫材料。通過催化氫化反應(yīng)將氫氣轉(zhuǎn)化為液態(tài)的四氫喹啉，易于儲(chǔ)存與運(yùn)輸。為了實(shí)現(xiàn)更溫和條件下的喹啉氫化，在前期工作的基礎(chǔ)上設(shè)計(jì)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(zhì)譜與X射線單晶衍射等手段對(duì)其結(jié)構(gòu)進(jìn)行了詳細(xì)地表征。進(jìn)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(shí)現(xiàn)了室溫下的喹啉氫化，幾乎定量地得到相應(yīng)的1,2,3,4-四氫喹啉。對(duì)喹啉底物進(jìn)行拓展，得到11種目標(biāo)產(chǎn)物，產(chǎn)率均不低于80%，展現(xiàn)出該催化體系具有優(yōu)異的反應(yīng)活性與廣泛的底物適用范圍。
關(guān)鍵詞：錳配合物；催化；喹啉；氫化；四氫喹啉
中圖分類號(hào)：O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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(huán)卡賓/金屬催化不對(duì)稱羰基加成反應(yīng)研究進(jìn)展
阮林新，施世良*
（中國科學(xué)院上海有機(jī)化學(xué)研究所金屬有機(jī)化學(xué)國家重點(diǎn)實(shí)驗(yàn)室，上海 200032）
摘要：近幾十年來，過渡金屬催化的不對(duì)稱反應(yīng)取得了顯著進(jìn)展。其中，不對(duì)稱羰基加成反應(yīng)因其能夠高效構(gòu)建C―C鍵并直接生成手性醇類化合物，受到廣泛關(guān)注。手性醇廣泛存在于藥物和天然產(chǎn)物結(jié)構(gòu)中，因此該類反應(yīng)在有機(jī)合成中具有重要價(jià)值。手性氮雜環(huán)卡賓（NHC）配體憑借其獨(dú)特的電子特性和空間結(jié)構(gòu)，在不對(duì)稱催化中展現(xiàn)出廣闊的應(yīng)用潛力。綜述了近年來NHC/金屬催化不對(duì)稱羰基加成反應(yīng)的研究進(jìn)展，包括酮、醛和亞胺等底物的不對(duì)稱芳基化、烯基化和烷基化反應(yīng)，以及動(dòng)態(tài)動(dòng)力學(xué)不對(duì)稱轉(zhuǎn)化等策略的開發(fā)。詳細(xì)討論了各類反應(yīng)的底物適用范圍、應(yīng)用研究及其反應(yīng)機(jī)理，并結(jié)合機(jī)理實(shí)驗(yàn)與密度泛函理論（DFT）計(jì)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(yīng)活性和實(shí)現(xiàn)對(duì)映選擇性控制中的關(guān)鍵作用。最后，總結(jié)了該領(lǐng)域目前面臨的挑戰(zhàn)，如不同類別底物間的反應(yīng)性差異、對(duì)映選擇性與非對(duì)映選擇性調(diào)控的局限性等，并對(duì)未來研究方向進(jìn)行了展望，以期為新型手性NHC配體的設(shè)計(jì)及其在不對(duì)稱催化中的進(jìn)一步應(yīng)用提供參考。
關(guān)鍵詞：不對(duì)稱催化；金屬催化；手性氮雜環(huán)卡賓配體；不對(duì)稱羰基加成；手性醇
中圖分類號(hào)：O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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(lián)咪唑啉的合成及在不對(duì)稱自由基偶聯(lián)反應(yīng)中的應(yīng)用
鐘誠成，陸展*
(浙江大學(xué) 化學(xué)系 土壤污染防治與安全全國重點(diǎn)實(shí)驗(yàn)室，浙江杭州 310058)
摘要：手性聯(lián)咪唑啉（BiIM）配體與手性雙?f唑啉（BOX）體系中的聯(lián)?f唑啉（BiOX）存在顯著的結(jié)構(gòu)同源性，其特征在于以氮原子替代氧原子構(gòu)筑核心骨架。這一結(jié)構(gòu)特征賦予BiIM配體獨(dú)特的化學(xué)屬性：通過在特定位置引入多樣化取代基，可實(shí)現(xiàn)對(duì)配位性能的精準(zhǔn)電子效應(yīng)調(diào)控，有效調(diào)節(jié)空間位阻參數(shù)與分子剛性，并為非均相催化體系的創(chuàng)新設(shè)計(jì)提供結(jié)構(gòu)基礎(chǔ)。自2001年Dupont研究團(tuán)隊(duì)首次完成BiIM配體的合成，Casey、宋毛平團(tuán)隊(duì)持續(xù)優(yōu)化合成方法，陸展課題組創(chuàng)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(gòu)建了結(jié)構(gòu)豐富的N-烷基及N-芳基聯(lián)咪唑啉配體庫。在不對(duì)稱催化領(lǐng)域，陸展團(tuán)隊(duì)率先將BiIM配體應(yīng)用于不對(duì)稱自由基交叉偶聯(lián)反應(yīng)體系，實(shí)現(xiàn)了芐位C-H鍵的高效芳基化、烯基化。此后，BilM在自由基反應(yīng)領(lǐng)域得到了廣泛的關(guān)注，無論是在二組分反應(yīng)還是在三組分反應(yīng)中都可以適用。盡管當(dāng)前BiIM配體在實(shí)際應(yīng)用中仍存在體系局限性，且自由基反應(yīng)固有的選擇性控制等問題亟待解決，但通過配體結(jié)構(gòu)的理性設(shè)計(jì)優(yōu)化，并結(jié)合計(jì)算化學(xué)模擬與高通量篩選技術(shù)，有望進(jìn)一步拓展其在藥物合成、復(fù)雜分子構(gòu)建等前沿領(lǐng)域的應(yīng)用潛力，為現(xiàn)代有機(jī)合成化學(xué)提供高效的催化策略與技術(shù)手段。
關(guān)鍵詞：手性聯(lián)咪唑啉；配體設(shè)計(jì)；不對(duì)稱催化；交叉偶聯(lián)反應(yīng)；自由基反應(yīng)
中圖分類號(hào)：O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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(jí)膦氧在不對(duì)稱氫化反應(yīng)中的研究進(jìn)展
趙夢(mèng)龍，韓召斌*
（中國科學(xué)院上海有機(jī)化學(xué)研究所金屬有機(jī)化學(xué)國家重點(diǎn)實(shí)驗(yàn)室，上海 200032）
摘要：不對(duì)稱氫化是制備手性化合物的重要手段，具有高原子經(jīng)濟(jì)性，高效高選擇性及環(huán)境友好等優(yōu)點(diǎn)。反應(yīng)使用的催化劑通常由過渡金屬和手性三價(jià)膦配體組成。由于三價(jià)膦單元對(duì)空氣和水極度敏感，增加了不對(duì)稱氫化的操作難度。二級(jí)膦氧（SPO）是一類結(jié)構(gòu)獨(dú)特的含磷化合物，其分子結(jié)構(gòu)存在五價(jià)磷形態(tài)的膦氧和三價(jià)磷形態(tài)的亞膦酸的互變異構(gòu)，在自由狀態(tài)下以對(duì)空氣和水穩(wěn)定的膦氧結(jié)構(gòu)存在，而與過渡金屬配位時(shí)則通常使用配位能力更強(qiáng)的三價(jià)磷形態(tài)。手性二級(jí)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(jié)構(gòu)可調(diào)性。二級(jí)膦氧與金屬配位后產(chǎn)生的磷-羥基官能團(tuán)可作為氫鍵的供體協(xié)助活化底物。手性二級(jí)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(jié)構(gòu)多樣的手性二級(jí)膦氧被設(shè)計(jì)合成出來，并應(yīng)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(duì)稱氫化中，取得了優(yōu)異的催化活性和對(duì)映選擇性，部分催化體系已在生物活性分子的高效不對(duì)稱合成中發(fā)揮作用。根據(jù)手性二級(jí)膦氧配體的結(jié)構(gòu)進(jìn)行分類，系統(tǒng)地總結(jié)了其作為配體在多種不飽和底物的不對(duì)稱氫化中的應(yīng)用進(jìn)展和存在的局限，并對(duì)后續(xù)的發(fā)展進(jìn)行了展望。
關(guān)鍵詞：二級(jí)膦氧；手性配體；不對(duì)稱氫化；互變異構(gòu)；過渡金屬
中圖分類號(hào)：O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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(huán)鈀催化劑的研究進(jìn)展
張潤通*1，陳俊1,2，馬保德1，張鳳2，陳根強(qiáng)*3
(1. 深圳職業(yè)技術(shù)大學(xué)碳中和技術(shù)研究院，廣東深圳 518055；2. 湖南農(nóng)業(yè)大學(xué) 化學(xué)與材料科學(xué)學(xué)院，湖南 長沙 410128；3. 南方科技大學(xué) a.前沿與交叉科學(xué)研究院，b.深圳格拉布斯研究院，廣東 深圳 518055)
摘要：環(huán)鈀催化劑是一類含有碳鈀鍵的鈀雜環(huán)催化劑。由于其結(jié)構(gòu)上的獨(dú)特性，在有機(jī)合成領(lǐng)域得到了廣泛的應(yīng)用。Hermann-Beller環(huán)鈀催化劑是環(huán)鈀催化劑的重要成員，它在Heck反應(yīng)、Suzuki偶聯(lián)反應(yīng)、Buchwald-Hartwig偶聯(lián)反應(yīng)、碳膦鍵偶聯(lián)反應(yīng)、羰基化反應(yīng)等多種反應(yīng)中得到了廣泛的應(yīng)用，但是目前還缺乏對(duì)該類環(huán)鈀催化劑的系統(tǒng)介紹與綜述。對(duì)Hermann-Beller環(huán)鈀催化劑在有機(jī)合成中的應(yīng)用和機(jī)理研究進(jìn)行系統(tǒng)而深入的綜述，并對(duì)未來的發(fā)展方向進(jìn)行了展望。
關(guān)鍵詞：Hermann-Beller環(huán)鈀催化劑；氧化偶聯(lián)反應(yīng)；碳膦鍵偶聯(lián)反應(yīng)；羰基化反應(yīng)；催化反應(yīng)機(jī)理
中圖分類號(hào)：O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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(yīng)中的應(yīng)用進(jìn)展
許冰1，張展鳴*2，張俊良*2
海軍軍醫(yī)大學(xué)藥學(xué)系上海 200433；2. 復(fù)旦大學(xué)化學(xué)系，上海 200438)
摘要：手性膦配體在不對(duì)稱催化反應(yīng)中發(fā)揮著核心作用，其膦原子上的取代基類型對(duì)反應(yīng)活性、化學(xué)選擇性及立體選擇性具有關(guān)鍵影響。富電子二環(huán)己基取代的膦結(jié)構(gòu)因優(yōu)異性能，已在多種手性配體中得到成功應(yīng)用并展現(xiàn)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(huán)己基膦基團(tuán)引入自主研發(fā)的Sadphos配體骨架，設(shè)計(jì)合成了一系列含二環(huán)己基單膦結(jié)構(gòu)的手性配體Xu-Phos。該類配體具有結(jié)構(gòu)簡潔、易于修飾的特點(diǎn)，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(yīng)用潛力的手性配體。綜述了近年來以Xu-Phos為優(yōu)勢(shì)手性配體開發(fā)的過渡金屬催化不對(duì)稱轉(zhuǎn)化反應(yīng)研究進(jìn)展。自2018年首次報(bào)道以來，鈀與Xu-Phos形成的催化體系穩(wěn)定性優(yōu)異，已成功驅(qū)動(dòng)一系列Heck反應(yīng)及其相關(guān)串聯(lián)反應(yīng)：通過烯烴、炔烴的對(duì)映選擇性Heck反應(yīng)，可高效構(gòu)建螺手性、中心手性及軸手性化合物；對(duì)于芳基碘化物連接的烯烴底物，其對(duì)映選擇性Heck反應(yīng)可通過還原、碳鹵鍵還原消除、Suzuki偶聯(lián)、Sonogashira 偶聯(lián)、親核鈀化、硼化及遠(yuǎn)程碳-氫烷基化等多種路徑終止，從而高化學(xué)選擇性、高立體選擇性地合成結(jié)構(gòu)多樣的苯并雜環(huán)衍生物。此外，Xu-Phos在鈀催化的烯烴碳胺化、碳醚化、分子內(nèi)碳?xì)滏I活化及消除反應(yīng)中亦表現(xiàn)出優(yōu)異的不對(duì)稱誘導(dǎo)能力，可精準(zhǔn)構(gòu)建多取代雜環(huán)化合物及軸向手性環(huán)己叉基骨架。除鈀催化體系外，Xu-Phos在其他金屬催化的不對(duì)稱反應(yīng)中也展現(xiàn)出良好應(yīng)用前景：在銅催化不對(duì)稱加成反應(yīng)中可高效合成手性芳基亞磺酰胺；作為手性單齒膦配體應(yīng)用于銥催化體系時(shí)，能實(shí)現(xiàn)酮與仲胺的直接不對(duì)稱還原胺化反應(yīng)。
關(guān)鍵詞：不對(duì)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(hào)： O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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(xué) 材料與化學(xué)化工學(xué)部，江蘇 蘇州 215006；2.國合通用測試評(píng)價(jià)認(rèn)證股份公司，北京 101407)
摘要：報(bào)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(fù)分解反應(yīng)，實(shí)現(xiàn)了目標(biāo)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(zhì)譜等分析方法對(duì)產(chǎn)物結(jié)構(gòu)和純度進(jìn)行了表征。深入研究了反應(yīng)時(shí)間、溫度、投料比、重結(jié)晶條件等關(guān)鍵工藝參數(shù)對(duì)產(chǎn)物產(chǎn)率的影響規(guī)律。結(jié)果表明，當(dāng)投料比控制為n(M-o-CH?C?H?NMe?):n(RECl?) = 2.95:1（M = Li/K）、反應(yīng)溫度為25 ℃、以THF為溶劑反應(yīng)2 h時(shí)，經(jīng)甲苯和正己烷的混合溶劑重結(jié)晶后，可獲得產(chǎn)率＞90%、單一稀土純度＞99%的目標(biāo)產(chǎn)物。通過精細(xì)化工藝調(diào)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(yīng)路徑兼具操作便捷性與工業(yè)可擴(kuò)展性，同時(shí)為其他稀土配合物的合成工藝開發(fā)提供了可借鑒的技術(shù)路線和實(shí)驗(yàn)依據(jù)，有望進(jìn)一步推動(dòng)稀土配合物在高端催化、新能源材料等領(lǐng)域的深度研發(fā)和實(shí)際應(yīng)用，為稀土資源的高值化利用提供技術(shù)支撐。
關(guān)鍵詞：稀土；稀土芐基配合物；工藝優(yōu)化；產(chǎn)率；純度
中圖分類號(hào)：O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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(xué)化學(xué)與分子工程學(xué)院，上海 200241）
摘要：α-炔基重氮酮作為一種重要的有機(jī)合成中間體，由于其既可以用作卡賓前體實(shí)現(xiàn)卡賓的反應(yīng)，又可以發(fā)生Wolff重排生成含有炔基的乙烯酮中間體參與后續(xù)轉(zhuǎn)化，近年來正逐漸受到關(guān)注。然而，現(xiàn)有的合成方法具有一定的局限性：僅限于使用預(yù)先制備的α-炔基酮并通過重氮轉(zhuǎn)移反應(yīng)得到對(duì)應(yīng)的α-炔基重氮酮。該方法具有以下缺點(diǎn)：1）綜合產(chǎn)率較低；2）步驟繁瑣需要多次溫度調(diào)控；3）反應(yīng)原料α-炔基酮穩(wěn)定性差，難以長期保存。因此，開發(fā)一種高效便捷的合成方法是必要的。基于此，設(shè)計(jì)了以α-芳基重氮Weinreb酰胺為關(guān)鍵前體的α-炔基重氮酮的合成策略。該策略具有官能團(tuán)耐受性良好，反應(yīng)條件溫和，步驟簡便，產(chǎn)率中等至優(yōu)異等優(yōu)點(diǎn)。同時(shí)，該策略也兼容炔丙基衍生物，為天然產(chǎn)物的衍生提供了平臺(tái)。
關(guān)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(hào)：O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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(jié)構(gòu)的氮雜環(huán)卡賓鈀配合物的合成及應(yīng)用
呂雷陽1，唐嘉偉1，王建軍2，羅偉??/font>2，廖志根3，關(guān)麗*1
（1. 中國人民大學(xué) 化學(xué)與生命資源學(xué)院 光轉(zhuǎn)換材料與生物光子學(xué)實(shí)驗(yàn)室，北京 100872；
2. 福建永晶科技股份有限公司 研發(fā)部，福建南平 354003）
3.福建省三明市清流縣高級(jí)職業(yè)中學(xué) 化工專業(yè)教研室，福建三明 365300）
摘要：氮雜環(huán)卡賓是一類具有強(qiáng)σ-供電子能力和立體電子效應(yīng)可調(diào)控的有機(jī)配體，在有機(jī)催化、過渡金屬催化、光催化合成以及功能材料制備等領(lǐng)域有著廣泛應(yīng)用。IPrBIDEA-Pd是一種獨(dú)特的咪唑型氮雜環(huán)卡賓鈀配合物，具有新穎的蝶烯結(jié)構(gòu)。與傳統(tǒng)氮雜環(huán)卡賓配合物相比，其咪唑環(huán)母體上引入形似蝴蝶翅膀的芳環(huán)，在催化過程中發(fā)揮著關(guān)鍵作用。該設(shè)計(jì)能有效限制芳胺環(huán)繞碳?氮鍵翻轉(zhuǎn)，抑制β?氫消除反應(yīng)及催化劑失活現(xiàn)象，從而顯著提升催化劑的周轉(zhuǎn)數(shù)、催化活性和反應(yīng)選擇性。詳細(xì)介紹了IPrBIDEA- Pd的設(shè)計(jì)、合成及其表征，通過幾個(gè)實(shí)例對(duì)其在有機(jī)合成中的應(yīng)用進(jìn)行了探討，涵蓋了偕二氟環(huán)丙烷的開環(huán)還原反應(yīng)及偶聯(lián)反應(yīng)、2-氟代烯丙基碳酸酯與烯丙基硼酸酯的交叉偶聯(lián)反應(yīng)、雜芳基氯參與的Suzuki-Miyaura反應(yīng)以及雜芳基二氯參與的Suzuki-Miyaura縮聚反應(yīng)。期望能夠進(jìn)一步開發(fā)IPrBIDEA配體及其衍生物和金屬配合物在合成化學(xué)、催化科學(xué)以及功能新材料構(gòu)建等學(xué)科領(lǐng)域的潛在應(yīng)用價(jià)值。
關(guān)鍵詞：氮雜環(huán)卡賓；鈀配合物；咪唑；有機(jī)合成；催化
中圖分類號(hào)：O626 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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(yī)大學(xué)藥學(xué)系，上海 200433；2. 復(fù)旦大學(xué) 化學(xué)系，上海 200438)
摘要：不對(duì)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(shí)現(xiàn)不對(duì)稱催化的關(guān)鍵。而“理想（IDEAL）”配體的設(shè)計(jì)開發(fā)，一直是合成化學(xué)家和工業(yè)界共同追求的目標(biāo)。在近十年來，基于“理想配體”設(shè)計(jì)理念，電性、骨架和邊臂多樣的新一代動(dòng)態(tài)自適應(yīng)型手性亞磺酰胺膦配體Sadphos家族被不斷的開發(fā)和應(yīng)用。目前，通過電性調(diào)節(jié)，改變配體膦原子的電負(fù)性和配體空間位阻，Xiang-Phos、Xu-Phos、TY-Phos依次被報(bào)道；通過骨架調(diào)節(jié)，改變配體配位基團(tuán)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(fā)；通過邊臂組裝，引入二苯基甲基膦，開發(fā)了一類手性叔丁基亞磺酰胺雙膦配體和多功能有機(jī)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(duì)稱Pictet?Spengler環(huán)化、C?S/C?P偶聯(lián)、Suzuki偶聯(lián)、動(dòng)力學(xué)拆分的去芳構(gòu)化、鈀雜烯丙基環(huán)加成和串聯(lián)Heck/Tsuji?Trost等反應(yīng)時(shí)表現(xiàn)出優(yōu)異的催化活性、化學(xué)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(shè)計(jì)和應(yīng)用，系統(tǒng)總結(jié)其自2017報(bào)道以來在過渡金屬催化的不對(duì)稱反應(yīng)中的研究進(jìn)展。
關(guān)鍵詞：膦配體；手性亞磺酰胺；不對(duì)稱催化；氧雜蒽骨架；Sadphos
中圖分類號(hào)： O62 文獻(xiàn)標(biāo)識(shí)碼：A 文章編號(hào)：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
