负载钯催化的Suzuki偶联反应研究进展

负载钯催化的Suzuki偶联反应,由于产物易分离、催化剂可重复使用,已引起人们的广泛关注.综述了近年来负载钯催化的Suzuki偶联反应研究进展,载体包括活性碳、金属氧化物、硅铝酸盐微孔分子筛、二氧化硅材料、活性粘土和聚合物等.     

乙二胺功能化纤维素负载纳米钯催化Suzuki反应的研究

以氯化纤维素为原料, 通过与乙二胺的胺化反应制得乙二胺功能化纤维素(Cell-EDA), 然后再将胺化纤维素在氯化钯乙醇溶液中反应可以方便制备得到乙二胺功能化纤维素负载的纳米钯催化剂(Cell-EDA-Pd0). 用SEM, TEM等分析方法对所制备的催化剂进行了表征; TEM分析表明乙二胺功能化纤维素负载的纳米钯呈球形, 粒径在10～20 nm左右. 实验结果表明, Cell-EDA-Pd0催化剂对空气稳定, 无需在惰性气体的保护下就能有效地催化芳基硼酸与卤代芳烃的Suzuki交叉偶联反应, 催化剂易回和收重复使用, 催化剂重复使用6次催化活性没有明显降低.     

高分子负载钯金属的非均相催化C—C偶联反应

本文主要介绍近年来高分子材料负载的钯金属在非均相催化C—C键偶联反应中的研究与应用。此类催化剂具有较高的活性、选择性和多次重复使用的稳定性,在催化反应膜器件、自动化的组合化学合成和实现向环境友好型的材料转化等方面有突出的发展前景。催化剂微囊化和纳米团簇化都是获取较高的活性和回收率的手段。使用高分子配体的优点是能直接固定金属,并通过不同的配位原子调节控制钯的活性,甚至呈现相应的小分子配合物不能催化的高分子效应,而高分子链本身还可以提供反应所需的良好机械性能和对不同反应介质的亲合性。     

无配体水介质中可循环聚乙烯吡咯烷酮负载钯催化Suzuki反应

In the absence of any ligand, a recoverable palladium（O） on poly（vinylpyrrolidone） （PVP） catalyzed Suzuki reaction of aryl iodide and bromide with potassium aryltrifluoroborate was developed. The reaction conditions involved the use of water as the solvent, potassium carbonate as the base, and PVP supported palladium metal colloids as the catalyst. The palladium metal could be recovered and recycled for eight consecutive trials without significant loss of its activity.     

水相钯催化Suzuki反应

钯催化的Suzuki反应是构建Csp2—Csp2键的主要方法之一,已广泛应用于医药、天然产物及先进功能材料等联芳类化合物的合成.近年来,水相Suzuki反应引起了人们的高度关注.对以纯水及水/有机混溶剂为介质的水相Suzuki反应的研究进展作一综述,特别是围绕如何解决水相Suzuki反应活性的问题,以催化体系为主线,重点介绍了水溶性配体/钯、表面活性剂、微波促进的非水溶性配体/钯及无配体钯等催化体系在水相Suzuki反应中的应用.     

磁性纳米粒子负载钯催化剂在C-C键偶联反应中的应用

磁性纳米粒子(MNPs)负载钯催化剂因具有高的催化活性及易于原位磁分离回收等优点而得到快速发展,成为一类具有广泛应用前景的纳米催化剂,在学术及工业领域均受到广泛的关注。 本文对近年来MNPs负载钯催化剂在Suzuki、Heck等C-C偶联反应中的应用研究进行简要阐述,并对其发展前景进行了展望。     

新型四齿膦配体在钯催化的Suzuki偶联反应中的应用

由廉价易得的1,2-环己二胺作为起始原料,通过简单的合成步骤制备了一种新型的四齿膦配体1,并将该配体应用于钯催化的Suzuki交叉偶联反应中.在仅为0.1 mol%的催化剂用量下,成功地实现了多种氯/溴代芳烃、氯/溴代杂环芳烃以及溴代烷烃底物与苯硼酸的交叉偶联反应,产率最高可达99%.     

水溶性亚胺配体/钯催化的室温 Suzuki 反应

 设计并合成了一种新型水溶性亚胺双齿配体 I, 并得到其单晶结构. 该配体具有半配位效应和绿色化学特征, 与氯化钯组成的催化体系在空气和室温条件下, 可有效催化乙醇水溶液中的溴代芳烃与芳基硼酸的 Suzuki 交叉偶联反应. 在 n(ArBr) = 0.5 mmol, n(ArB(OH)₂) = 0.75 mmol, x(PdCl₂) = 1%, x(I) = 2%, n(K₂CO₃) = 1.0 mmol, c(EtOH) = 50% 水溶液的优化条件下, 经 20 min 反应, 分离收率即可达到 99%.     

正电性磁性氧化铁胶粒负载钯催化的Suzuki偶联反应

发展了一种超顺磁性Fe3O4纳米粒子负载Pd0的简易方法. 利用Fe3O4溶胶带正电荷的特性, 将负离子 通过静电作用吸附在Fe3O4胶体粒子表面( /Fe3O4), 以抗坏血酸(Vc)进一步还原即得到载有金属Pd团簇的Fe3O4胶体粒子(Pd0/Fe3O4). 该磁性载体负载的Pd催化剂对Suzuki反应表现出良好的催化活性, 且在反应后, 可方便地通过永久磁铁将催化剂从反应体系中分离出来, 进行循环使用. 试验表明, 该催化剂在循环使用五次后反应活性无明显下降. 进一步试验发现, 这种磁性纳米粒子负载的金属钯对一系列卤代芳烃的Suzuki偶联反应均表现出较优的催化活性.     

Microwave-promoted Palladium Catalyzed Suzuki Cross-coupling Reaction in Water

Suzuki coupling is probably the most versatile approach among the cross-coupling reactions and the reaction has long been the subject of intensive work in the area of transition-metal chemistry1. In recent years, various modifications involving the catalyst, solvents, bases, reaction conditions and synthetic technique have been developed 2. The Suzuki cross-coupling reaction in water is more safe, economical. It is an environmentally friendly alternative in organic synthesis. The use of w…     

Microwave-assisted Palladium-micelle-catalyzed Suzuki Cross-coupling Reaction in Water

A microwave-accelerated Suzuki coupling procedure was developed via guanidinium ionic liquids(GILs) stabilized Pd-micelle.The Pd micelle/GILs play a key role in enhancing the activity,due to the highly dispersed Pd active sites and the phase transfer function of GILs,which ensures the adsorption of reactants and facilitates the translation of the intermediates to the surface of the micelle.     

Simultaneous Reduction of Aldehyde Group to Hydroxymethyl Group in Palladium-catalyzed Suzuki Cross-coupling Reaction

The authors presented an efficient method for the palladium-catalyzed Suzuki cross-coupling reaction with the simultaneous reduction of the aldehyde to a hydroxymethyl group.This method allows halide substituted aryl aldehydes to readily react with arylboronic acids,producing polycyclic aromatic alcohols in moderate to good yields.The reaction was catalyzed by Pd（OAc）2（3％,molar fraction） at 150 ℃ in the presence of 6％（molar fraction）1,4-diazabicyclo[2.2.2]octane（DABCO） and 3 times the molecular weight of K2CO3 in the mixture solvent of N,N-dimethylformamide（DMF）/H2O [V（DMF）∶ V（H2O）=5∶1].     

光催化Suzuki偶联反应的非均相催化剂研究进展

Suzuki偶联反应作为构建C-C键的最有效的手段之一,在医药、染料和电子工业等领域扮演着重要的角色.近年来,光催化技术和绿色有机合成化学蓬勃发展,利用可再生的太阳能光催化Suzuki偶联反应不但可以解决在催化反应过程中的能源与环境问题,还可以在温和条件下高产率地获得联苯化合物.与均相光催化剂相比,非均相光催化剂具有良...     

羧基亚胺配体的合成及其促进Suzuki偶联反应的研究

合成了4种羧基亚胺配体并将其用于促进Suzuki偶联反应。通过考察配体结构、溶剂极性、碱强度和温度等因素对反应产率的影响,确定了羧基亚胺配体参与的钯催化Suzuki偶联反应的最佳条件为:催化剂的量为0.001(mol)%的Pd Cl2和0.002(mol)%的配体,以碳酸钾作碱,4m L乙醇水溶液(1∶1,体积比)作溶剂,反应温度为60℃,在空气条件下反应。结果表明,羧基亚胺配体能够有效促进Suzuki偶联反应;在合成的配体L1~L4中,具有适当的位阻和给电子基团的L2的催化活性最高,能够高效催化合成一系列联芳类化合物。     

Aryl-guanidine/Pd-catalyzed Suzuki Cross-coupling Reaction at Room Temperature

Four aryl-guanidines(AG)were synthesized and used for the palladium-catalyzed Suzuki cross-coupling reaction to test the catalytic activity.In the presence of steric bulk AG,when aryl bromide and arylb...     

Mixed Linker Metal Organic Framework as an Efficient and Reusable Catalyst for Suzuki Miyaura Coupling Reaction

Series of metal organic frameworks from nitrogen based ligand were synthesized as efficient and reusable catalyst via mixed linker methods. The thermogravimetric study of the mixed linker metal organic framework (MIXMOF) reveals that the complexes are potential thermally stable materials. The palladium supported catalysts exhibits high catalytic activity toward the Suzuki-Miyaura cross coupling reaction and can be reused several times without any visible loss of activity even after five consecutive times.     

Palladium Catalyzed Suzuki Cross-coupling Reaction in Molten Tetra-n-butylammonium Bromide

A practical procedure for palladium catalyzed Suzuki cross-coupling reaction of arylboronic acids with aryl halides, including aryl chlorides in molten tetra-n-butylammonium bromide (TBAB) was developed. The reaction exhibits high efficiency and functional group tolerance. The recovery of the catalyst and molten n-Bu4NBr was also investigated.     

Synthesis and application of ortho-palladated complex of (4-phenylbenzoylmethylene)triphenylphosphorane as a highly active catalyst in the Suzuki cross-coupling reaction

The ortho-metallated complex [Pd(μ-Cl){κ₂(C,C)-[C₆H₄(PPh₂CHC(O)C₆H₄-Ph-4)}]₂ (2a) was prepared by refluxing of Pd(OAc)₂ and {(Ph)₃PCHCOC₆H₄-Ph-4} (PhBPPY) of in CH₂Cl₂ followed by addition of an excess of KCl in MeOH Complex (2a) reacts with triphenylphosphine to give the mononuclear derivative [Pd(Cl)(PhC₆H₄COCHPPh₂C₆H₄)(PPh₃)] (3a) whose crystal structure has been determined by single crystal X-ray diffraction. The Suzuki reactions of aryl bromides and chlorides of varying electron density using complex (3a) as an efficient catalyst were performed, giving the cross-coupling products in good to excellent yields.