Palladium(II)-N-heterocyclic carbene complex derived from proline towards Suzuki-Miyaura coupling reaction in water at room temperature

Palladium(II)-N-heterocyclic carbene complex 1 derived from proline has been proved to be a highly effective catalyst in the Suzuki-Miyaura coupling reaction of aryl iodides and bromides with arylboronic acids in water at room temperature. The reactions are tolerant towards various functional groups in the substrates. Moreover, the complex 1-catalyzed medium-scale (10.0 mmol) Suzuki-Miyaura reactions were also carried out and it was found that the complex was also effective enough in these cases.     

Pd-CNT-catalyzed ligandless and additive-free heterogeneous Suzuki-Miyaura cross-coupling of arylbromides

Pd-CNT efficiently catalyzed Suzuki-Miyaura coupling of arylbromides under ligandless and additive-free conditions in aqueous media. For hydrophilic substrates, the reaction could be carried out in neat water.     

Palladium-catalyzed cross coupling reaction of N-alkoxyimidoyl bromides and its application to one-pot synthesis of N-arylamines

The synthetic utility of N-alkoxyimidoyl halides is demonstrated using the palladium-catalyzed cross-coupling reaction. The Sonogashira and Suzuki-Miyaura coupling reactions of N-alkoxyimidoyl bromides produced versatile ketoxime ethers in good to excellent yields. A one-pot reaction of the imidoyl bromides with arylboronic acid and allylmagnesium bromide to produce N-arylamines via Suzuki-Miyaura coupling followed by domino reaction involving sequential addition-eliminative rearrangement-addition reactions was developed.     

Heterogeneous Pd/C-catalyzed ligand-free, room-temperature Suzuki-Miyaura coupling reactions in aqueous media

A mild and efficient ligand-free Suzuki-Miyaura coupling reaction catalyzed by heterogeneous Pd/C was developed. Aryl bromides and triflates undergo the cross-coupling with aryl boronic acids in excellent yields without the presence of any additives in aqueous media at room temperature. Aryl vinyl boronic acids are also applicable to this coupling reaction and provide the trans-stilbene derivatives in high yields. The application of wet-type Pd/C to the coupling reaction was achieved without any loss of activity under aerobic conditions, and the reuse of Pd/C is feasible for a fifth run without significant loss of activity. Inductively coupled plasma (ICP) mass-spectrometric analysis of the filtrate from the reaction mixture of 4-bromonitrobenzene with phenylboronic acid demonstrated that the palladium metal hardly leached into the solution within the limits of the detector (<1 ppm), thus suggesting that the present Suzuki-Miyaura reaction proceeded by heterogeneous catalysis.     

An efficient Pd(II)-(2-aminonicotinaldehyde) complex as complementary catalyst for the Suzuki-Miyaura coupling in water

An efficient new Pd(II)-(2-aminonicotinaldehyde)-catalyzed Suzuki-Miyaura coupling of the aryl halides (Br, Cl and I) and organoboronic acids at moderate temperature in water is described. Low catalyst loading, easy accessibility, being an air-stable catalyst, functional group compatibility, and water as the reaction medium are some of the key features of this synthetic method. This protocol is also applicable for gram scale.     

Heterogeneous Suzuki and copper-free Sonogashira cross-coupling reactions catalyzed by a reusable palladium(II) complex in water medium

A new polystyrene anchored Pd(II) azo complex has been synthesized and characterized. The present Pd(II) azo complex behaves as a very efficient heterogeneous catalyst in the Suzuki coupling and Sonogashira coupling reaction in water medium. Aryl halides, coupled with phenylboronic acids (Suzuki-Miyaura reaction) or terminal alkyne (Sonogashira reaction), smoothly afford the corresponding cross-coupling products in excellent yields (83-100% yield for Suzuki reaction and 68-96% yield for Sonogashira reaction of aryl halides) under phosphine-free reaction conditions in the presence of polystyrene anchored Pd(II) azo complex catalyst in water medium. Furthermore, the catalyst has shown good thermal stability and recyclability. This polymer-supported Pd(II) catalyst could be easily recovered by simple filtration of the reaction mixture and reused for more than six consecutive trials without a significant loss of its catalytic activity.     

Iron-catalyzed alkyl-alkyl suzuki-miyaura coupling

Chemoselective Suzuki-Miyaura coupling of primary and secondary alkyl halides is realized by using an iron/Xantphos catalyst. Primary and secondary alkyl bromides undergo the reaction to give the coupling products in good yields. Application to the synthesis of long-chain fatty acid derivatives is also described.     

Palladium catalyzed Heck-Mizoroki and Suzuki-Miyaura coupling reactions (Review)

This article is about the progress of palladium compounds as a catalyst for Heck-Mizoroki and Suzuki-Miyaura coupling reactions. Industrial catalysts with broad applicability need continuous catalyst development process through modification of ligand design, geometry and functionality. Recently catalysts have been synthesized through attachment of the activated palladium complexes on the surface of polymer support, particularly, insoluble in reaction medium. An appropriate mixture of palladium salt and ligand is also used as an important modification in some cases to get better results. We surveyed the important palladium compounds synthesized up to early 2014 for Heck-Mizoroki and Suzuki-Miyaura coupling reactions and summarize their progress in terms of ligand modification and other associated parameters.     

P,N-Type benzimidazolyl phosphine ligands for the palladium-catalyzed Suzuki coupling of potassium aryltrifluoroborates and aryl chlorides

This study describes the efficacy of P,N-type benzimidazolyl phosphine ligands, which can be easily synthesized from commercially available and inexpensive starting materials. The application of this ligand array in palladium-catalyzed Suzuki-Miyaura coupling reaction of aryl chlorides with potassium aryltrifluoroborates is described. The air stable benzimidazolyl phosphines in combination with a palladium metal precursor provides highly effective catalysts for the Suzuki-Miyaura coupling of unactivated aryl chlorides and can achieve a catalyst loading of only 0.05 mol %.     

浅谈国外“Suzuki-Miyaura金属偶联反应”的教学设计思路

Suzuki-Miyaura金属偶联反应是在零价钯配合物的催化下,芳基硼酸或硼酸酯与卤代芳烃发生交叉偶联的过程。该反应具有很强的底物适应性和官能团容忍性,广泛应用于众多天然产物与有机材料的合成。鉴于反应的重要性,近年来国外高校逐渐尝试将Suzuki-Miyaura反应引入到本科生的有机实验教学中。本文针对2000年后Journal of Chemical Education期刊中涉及的Suzuki-Miyaura反应,分别从反应条件、后处理和表征方法、实验拓展等多个方面进行了比较和归纳,并对其设计理念和教学特色进行了综述。     

用于Suzuki-Miyaura反应的阴离子交换树脂负载钯催化剂(英文)

以碱性阴离子交换树脂Amberlite IRA-900为载体,Pd(C3H5)(C5H5)为金属有机前体,采用金属有机气相沉积法在室温下制备了Pd@IRA-900多相催化材料.紫外-可见光谱分析证明前体和树脂骨架之间的化学作用以及树脂本身的孔道结构使得Pd纳米粒子均匀分散在载体上.透射电镜结果显示钯纳米粒子的平均尺寸为2.6 nm.在较温和的条件下Pd@IRA-900对多种卤代芳烃和苯硼酸的Suzuki偶联都具有良好的催化活性,并且催化剂重复使用5次之后依然具有很好的活性.此外,对树脂载体进行碱性交换处理后可得到一种双功能催化材料Pd@IRA-900(OH),该催化剂在不加入碱的条件下也可以催化碘苯和苯硼酸的Suzuki偶联反应.     

An expeditious aqueous Suzuki-Miyaura method for the arylation of bromophenols

The development of a novel Suzuki-Miyaura method has been achieved to allow the efficient arylation of bromophenols. A range of functionality is tolerated with regard to the boronic acid coupling partner and the reaction exhibits complete chemoselectivity for the C_aryl-Br bond versus the C_aryl-Cl bond in the aryl halide input. The experimental protocol features a short reaction time of 15 min, utilizes inexpensive Pd/C as a catalyst, and is conducted with water as the solvent.     

Palladium(0) deposited on PAMAM dendrimers as a catalyst for C-C cross coupling reactions

PAMAM dendrimers of generations G2-G3 as well as a partially substituted derivative of generation G4 and a low-molecular-weight tricyclic ligand 4 were used to bind Pd(0) nanoparticles. The obtained adducts were tested as catalysts for C-C cross-coupling reactions, such as the Suzuki-Miyaura, Hiyama, Heck and Sonogashira reaction. The highest yields of the coupling product, diphenylacetylene, were obtained with all the catalysts studied in the Sonogashira coupling performed in ethanol with K?CO? as base. Very good results, 85-100%, were also found in the Suzuki-Miyaura cross-coupling, while the efficiency of the Hiyama coupling appeared lower, with 38-52% of 2-methylbiphenyl formed. In all reactions, the G2-Pd(0) catalyst, containing an unmodified dendrimer, afforded the highest yields of the cross-coupling products.     

Bis-diimidazolylidine complexes of nickel: investigations into nickel catalyzed coupling reactions

Air and moisture stable homoleptic bis(diimidazolylidine)nickel(II) complexes, ([(diNHC)(2)Ni](2+)) 3a,b and their corresponding silver(I) 4a,b and palladium(II) 5a,b complexes were synthesized and characterized by NMR and single crystal X-ray analysis. The catalytic potential of complex 3a was assessed in Mizoroki-Heck and Suzuki-Miyaura coupling reactions. In the Suzuki-Miyaura coupling reaction, nickel precatalyst 3a was active for the coupling of aryl chlorides as well as aryl fluorides. The analogously synthesized Pd(II) complexes resulted in formation of (diNHC)PdCl(2) species which were not active for the coupling of aryl fluorides. For the Mizoroki-Heck reaction, it was found that aryl iodides could be activated in the absence of nickel or palladium precatalysts when using Na(2)CO(3) or NEt(3) as base while aryl iodides and aryl bromides could be activated in the Suzuki-Miyaura reaction sans precatalyst when K(3)PO(4) was used as base.     

Pd-catalyzed regioselective and stereospecific Suzuki-Miyaura coupling of allylic carbonates with arylboronic acids

The Pd-catalyzed Suzuki-Miyaura coupling reaction of unsymmetric 1,3-disubstituted secondary allylic carbonates with arylboronic acids has been developed in a wet solvent under a base-free system to afford allyl-aryl coupling products in a high level of isolated yields with complete regio- and E/Z-selectivities with good to excellent chemoselectivities. The coupling reaction of optically active allyl carbonates gave allyl-aryl coupling products with excellent enantioselectivities with inversion of the stereochemistry. This coupling method was successfully applied to the synthesis of (S)-naproxen.     

An amphiphilic resin-supported palladium catalyst for high-throughput cross-coupling in water

[reaction: see text] The Suzuki-Miyaura coupling of aryl halides (8 varieties) and aryl- or vinylboronic acids (12 varieties) took place in water in the presence of a palladium complex of an amphiphilic polystyrene-poly(ethylene glycol) copolymer resin-supported N-anchored 2-aza-1,3-bis(diphenylphosphino)propane ligand and potassium carbonate to give uniform and quantitative yields of the corresponding biaryls (96 varieties).     

钯纳米颗粒负载在聚苯胺材料上制得催化Suzuki-Miyaura偶联反应的高效催化剂

在最近的几十年里,金属钯催化的Suzuki-Miyaura偶联反应已经得到了越来越多的关注,被广泛应用于药物、天然产物以及新材料的合成.与此同时均相催化剂发展迅速,高效的配体和大量的设计被用于Suzuki-Miyaura偶联反应中,但是钯催化剂的配体通常很昂贵和难以合成,因此钯催化剂系统的回收是非常有价值的,不仅是经济上的原因,同时也避免了产品的污染,所以发展非均相催化剂是必要的.近年来,研究学者们致力于设计非均相的钯催化剂,如将钯纳米颗粒负载到金属有机骨架、介孔分子筛以及活性炭等多种材料上得到的非均相钯催化剂并应用于Suzuki-Miyaura偶联反应中.我们主要介绍了钯纳米颗粒被负载在含磷配体的交联的聚苯胺材料上制得负载的钯催化剂,首先通过钯催化的三(4-碘苯基)胺与金刚烷基膦的C–P偶联,再由钯催化三(4-碘苯基)胺与对苯二胺的C–N偶联,进而得到钯纳米颗粒负载在含金刚烷基膦的聚苯胺材料上的催化剂Pd@PAN-Ad-0.5(钯含量为0.58 wt%),同时我们对催化剂进行了一些表征,如TEM,SEM,XRD,EDX,XPS,FT-IR,ICP等.通过TEM分析,我们发现钯纳米颗粒在聚合物表面分布均匀,并且金属钯的平均粒径为2–3 nm;EDX检测显示催化剂含有C,N,P,Pd,I元素,说明钯负载到含金刚烷基膦的聚苯胺材料上的催化剂Pd@PAN-Ad-0.5已经形成,并被用于Suzuki-Miyaura偶联反应.我们对反应体系中的各种影响因素进行了优化,包括溶剂、碱、反应时间、催化剂加入量以及不同的催化剂的优化,最终确定了最佳反应条件;对于带有不同取代基(如腈基、甲氧基、醛基、酮基以及硝基)的氯代芳烃和溴代芳烃与苯硼酸的Suzuki-Miyaura反应,以较少的催化剂使用量(0.075 mol%Pd)就能获得较高的相应的联苯产物收率.此外,催化剂Pd@PAN-Ad-0.5在偶联反应中具有较高的反应活性的同时,还具有较好的回收使用能力(至少能够回收使用5次),循环使用4次以后还具有较高的催化活性.为了探索催化剂Pd@PAN-Ad-0.5在工业上的应用,由于4'-氯-2-硝基-1,1'-联苯是合成啶酰菌胺药物的重要中间体,因此我们使用催化剂Pd@PAN-Ad-0.5催化2-硝基氯苯与4-氯苯硼酸的偶联反应,目标产物4'-氯-2-硝基-1,1'-联苯的收率高达96%.我们相信这类催化剂应用于实验室或工业上合成联苯化学品具有较大的潜力.     

A versatile palladium catalyst system for Suzuki-Miyaura coupling of alkenyl tosylates and mesylates

A general and effective palladium system for Suzuki-Miyaura coupling of alkenyl electrophiles under mild reaction conditions is reported. With the Pd(OAc)(2)/CM-phos system, a variety of alkenyl tosylates are coupled well with ArB(OH)(2). Moreover, the first successful examples of using alkenyl mesylates in alkenylation are also described.     

An efficient and general synthesis of 3-substituted propionaldehydes using the Suzuki-Miyaura coupling

An efficient method to prepare 3-substituted propionaldehyde derivatives using a Suzuki-Miyaura coupling is reported. The reaction has been demonstrated on a range of substrates including several where the Heck reaction with allyl alcohol failed to give the desired aldehyde product.     

A novel water-soluble NHC-Pd polymer: an efficient and recyclable catalyst for the Suzuki coupling of aryl chlorides in water at room temperature

A novel water-soluble NHC-Pd polymer with triethylene glycol legs was developed as a water soluble and highly recyclable catalyst that shows high catalytic activity in the Suzuki-Miyaura coupling of aryl chlorides in high yields in water at room temperature.