- A recyclable heterogeneous nanocatalyst of copper-grafted natural asphalt sulfonate (NAS@Cu): Characterization, synthesis and application in the Suzuki-Miyaura coupling reaction
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A new and efficient nanocatalyst was identified, synthesized and introduced and its catalytic activity was investigated in the Suzuki coupling reaction. This nanocatalyst can be synthesized by sulfonating natural asphalt as a high-carbon, cost-effective and accessible substrate using high-concentration sulfuric acid. After being neutralized by NaOH, it was transformed into sodium natural asphalt sulfonate (Na-NAS). Ultimately, the nanocatalyst was synthesized through a displacement reaction of sodium natural asphalt sulfonate with copper chloride. The solid derived (NAS@Cu) was identified using Transmission Electron Microscopy (TEM), Energy Dispersive Spectroscopy (EDS), Scanning Electron Microscopy (SEM), N2 sorption isotherms, Inductively Coupled Plasma (ICP), X-ray Diffraction (XRD), Thermogravimetric Analysis (TGA), Atomic Absorption Spectrometry (AAS) and Fourier-transform Infrared spectroscopy (FT-IR). NAS@Cu is a heterogeneous catalyst with advantages such as having a high specific surface area, being environmentally friendly and economically sound and simple purification and separation from the reaction mixture. Moreover, the nano-catalyst was recycled several times without any significant changes in its catalytic properties. This journal is
- Kohzadi, Homa,Soleiman-Beigi, Mohammad
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- Extended architectures constructed of thiourea-modified SBA-15 nanoreactor: A versatile new support for the fabrication of palladium pre-catalyst
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We designed and synthesized a novel catalyst consisting of ordered mesoporous silica (SBA-15) functionalized with bis(thiourea) (BTU) linker. The regular and unique pore channels of BTU-SBA-15 ensure proper control of the size and homogeneous distribution of palladium nanoparticles. The physiochemical properties of the hybrid Pd?BTU-SBA-15 pre-catalyst were investigated using various techniques. The proposed catalyst is found to be very active, reusable, stable and scalable, and has excellent reactivity and selectivity for Suzuki and Heck coupling reactions under very mild and sustainable reaction conditions.
- Alamgholiloo, Hassan,Noroozi Pesyan, Nader,Rostamnia, Sadegh
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- The Suzuki reaction under solvent-free conditions
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The coupling reaction of diverse arylhalogenids with phenylboronic acid under solvent-free conditions has been performed using a palladium catalyst. The order of reactivity was complementary to the normal Suzuki reaction.
- Nielsen,Peters,Axelsson
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- Cross-Linked Thiazolidine Network as Support for Palladium: A New Catalyst for Suzuki and Heck Reactions
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A thiazolidine-based material was used for the first time as support for palladium. The support was prepared by starting from a highly cross-linked thiazolium-based material, obtained by radical oligomerization of a bisvinylthiazolium dibromide salt in the presence of 3-mercaptopropyl-modified silica SBA-15. Palladium was immobilized by treatment with tetrachloropalladate salt. Reduction with sodium borohydride afforded a thiazolidine-based material that acted as ligands for the Pd species. The thiazolidine-based palladium catalyst was fully characterized and, working in only 0.1 mol% amount, displayed good activity in the Suzuki-Miyaura and in the Heck reactions. Several biphenyl and alkene compounds could be prepared in high yields. The catalytic material proved to be fully recoverable and it was representatively used for three times in the Suzuki-Miyaura reaction without showing any decrease in its activity.
- Bivona, Lucia Anna,Giacalone, Francesco,Vaccaro, Luigi,Aprile, Carmela,Gruttadauria, Michelangelo
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- Immobilized palladium on modified magnetic nanoparticles and study of its catalytic activity in suzuki-miyaura C-C coupling reaction
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A new magnetically reusable nanosolid, Fe3O4@PPCA@Pd(0) (PPCA = piperidine-4-carboxylic acid), as a versatile and highly effective catalyst was fabricated and characterized using transmission and scanning electron microscopies, X-ray diffraction, thermogravimetric analysis, Fourier transform infrared and energy-dispersive spectroscopies and vibrating sample magnetometry. This nanosolid shows great catalytic activity for the synthesis of biphenyl compounds in short reaction times and with high yields. The magnetic character of this catalyst allows retrieval and multiple uses without appreciable loss of its catalytic activity. Our system not only solves the basic problems of catalyst separation and recovery, but also the reactions can be performed in green media.
- Azadi, Gouhar,Ghorbani-Choghamarani, Arash
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- Pd(OAc)2 in WERSA: A novel green catalytic system for Suzuki-Miyaura cross-coupling reactions at room temperature
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A recyclable/reusable Pd(OAc)2 catalysed Suzuki-Miyaura cross-coupling reaction condition in neat "Water Extract of Rice Straw Ash" (WERSA) at room temperature was developed. This is a ligand/base/promoter/additive/organic media free protocol.
- Boruah, Preeti Rekha,Ali, Abdul Aziz,Chetia, Mitali,Saikia, Bishwajit,Sarma, Diganta
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- Nitrogen-doped graphdiyne for effective metal deposition and heterogeneous Suzuki-Miyaura coupling catalysis
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For heterogeneous catalysts with nitrogen doped carbon materials as supporting substrates, accurate nitrogen (N) species and content is an important factor for promoting the catalytic activity. In this paper, N-doped graphdiyne (NGDY) was prepared from tetraethynylpyrazine (TEP) by bottom-up synthesis method as the support of metal nanoparticles. Specific pyridine nitrogen atoms are introduced in the N-doped carbon material. This unique structure makes it a promising material to support ultrafine metal particles or clusters. Microwave-assisted anchoring of Pd, Pt, Cu, Ni nanoparticles on NGDY generated novel hybrid composites, in which Pd-NGDY has high versatility for Suzuki-Miyaura reaction. DFT calculations revealed a charge transfer from NGDY to Pd NPs, and the free energy distribution showed a downward trend for Suzuki-Miyaura coupling reactions.
- He, Feng,He, Jingyi,Li, Yongjun,Li, Yuliang,Shen, Han,Xue, Yurui
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- Metformin as a versatile ligand for recyclable palladium-catalyzed cross-coupling reactions in neat water
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We present the high catalytic activity of an in situ generated palladium(ii)/metformin complex in neat water for the Suzuki-Miyaura and Sonogashira cross-coupling reactions. These reactions were performed in pure water without any co-solvent or mass transfer agent. The palladium(ii)/metformin complex gave excellent to good yields for the Suzuki-Miyaura coupling reaction and catalyzed with a certain specificity to the aryl iodide coupling in the Sonogashira reaction. The methodology showcases a recyclability up to four catalytic runs for the Suzuki-Miyaura cross-coupling reaction, performed with only 0.5 mol% palladium loading.
- Fortun,Beauclair,Schmitzer
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- Pd(OAc)2@SBA-15/PrEn nanoreactor: A highly active, reusable and selective phosphine-free catalyst for Suzuki-Miyaura cross-coupling reaction in aqueous media
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A series of ordered mesoporous organic-inorganic hybrid material was designed by using the amine-functionalized SBA-15 (PdX2@SBA-15/N Y, Y = 1, 2) as solid support for palladium complexes. Among them, the Pd(OAc)2/ethylenediamine complex encapsulated into SBA-15 (Pd(OAc)2@SBA-15/PrEn or Pd(OAc)2@SBA-15/PrNHEtNH 2) exhibits higher activity and selectivity toward Suzuki cross-coupling reaction under aerobic conditions and water solvent mixture. The SBA-15/PrEn supported palladium pre-catalyst could be separated easily from reaction products and used repetitively several times, showing its superiority over homogeneous catalysts for industrial and chemical applications. Copyright
- Rostamnia, Sadegh,Xin, Hongchuan
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- A new functionalized mesoporous matrix supported Pd(ii)-Schiff base complex: An efficient catalyst for the Suzuki-Miyaura coupling reaction
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A new Pd(ii) bounded 2D-hexagonally ordered functionalized MCM-41 type material (IV) has been synthesized. Functionalization was carried out by the anchoring of 3-aminopropyltriethoxysilane in the MCM-41 type mesoporous material, followed by grafting with 2,6-diacetylpyridine (DAP) to give a N 3-type Schiff base chelating attachment for the Pd(ii) species. Fourier transform infrared (FTIR), powder X-ray diffraction (PXRD) and high resolution transmission electron microscopy (HRTEM) studies have been used to characterize the material. Material IV behaves as a highly active catalyst towards Suzuki-Miyaura cross-coupling reaction for the synthesis of biaryl organics. In addition, IV acts as a true heterogeneous catalyst in coupling reaction. It was found that this catalyst is highly efficient and recyclable towards Suzuki-Miyaura reaction with high turn over frequencies. X-Ray photoelectron spectroscopic (XPS) analysis was employed to understand the oxidation state of the palladium atom in the catalyst (IV) and its loading in the material. The Royal Society of Chemistry.
- Dhara, Koushik,Sarkar, Krishanu,Srimani, Dipankar,Saha, Subrata Kumar,Chattopadhyay, Pabitra,Bhaumik, Asim
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- Suzuki-Miyaura cross-coupling reaction catalyzed by a highly stable Pd(P-Phos)Cl2 complex at room temperature under air
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A new Pd(P-Phos)Cl2 complex was synthesized and characterized by 1H NMR, 13C NMR, 31P NMR, and X-ray single crystal structure determination. The complex proved to be a highly stable and efficient catalyst for substrates with a wide range of functional groups in Suzuki-Miyaura cross-coupling reactions under air at room temperature. Low catalyst loadings were employed and turnover number of up to 49000 was obtained.
- Ge, Yicen,Cheng, Yujing,Fu, Haiyan,Zheng, Xueli,Li, Ruixiang,Chen, Hua,Li, Xianjun
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- Support-free palladium-NHC catalyst for highly recyclable heterogeneous suzuki-miyaura coupling in neat water
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Among the various new challenges of chemical processes in water, research on stable, highly active, and recyclable catalysts is a prosperous field. We present here a palladium-NHC catalyst that was synthesized with good yields through a series of simple synthetic steps. This organometallic species was used as a heterogeneous catalyst in low loadings for Suzuki-Miyaura coupling in neat water, under mild conditions. Reaction conditions were optimized for a simple, green, and support-free procedure, without using any phase transfer agent. The catalyst shows excellent reactivity in short times toward different substrates and a very good recyclability.
- Charbonneau, Mathieu,Addoumieh, George,Oguadinma, Paul,Schmitzer, Andreea R.
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- Highly efficient copper(0)-catalyzed Suzuki-Miyaura cross-coupling reactions in reusable PEG-400
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Readily available copper powder with K2CO3 as the base was extremely effective catalyst for Suzuki-Miyaura coupling reaction performed in PEG-400, which afforded almost quantitative coupling products of aryl iodides. Using iodine as additive, coupling products of aryl bromides or chlorides could be obtained with moderate to good yields.
- Mao, Jincheng,Guo, Jun,Fang, Fubing,Ji, Shun-Jun
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- 'On-water' organic synthesis: A green, highly efficient, low cost and reusable catalyst system for biaryl synthesis under aerobic conditions at room temperature
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A simple, greener, efficient, low cost and mild protocol has been developed for sucrose assisted palladium-catalyzed Suzuki reactions in water at room temperature under aerobic conditions. The results demonstrate that the sucrose played a crucial role making this protocol highly efficient. The PdCl2/sucrose/K2CO3/H2O system showed superb catalytic activity towards the Suzuki reaction of a wide range of aryl/heteroaryl halides with different substituted phenylboronic acids. This method offers an attractive alternative to the existing protocols since the reaction proceeds in aqueous media at room temperature with operational simplicity, shorter reaction time, cost-effectiveness and provides the products in high yields. The catalytic system is highly recyclable, allowing the reuse of the palladium catalyst in subsequent catalytic runs without significant loss of activity.
- Saikia, Bishwajit,Boruah, Preeti Rekha,Ali, Abdul Aziz,Sarma, Diganta
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- Suzuki coupling reactions catalyzed by Schiff base supported palladium complexes bearing the vitamin B6 cofactor
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Novel Schiff bases were synthesized by condensing aromatic amines with pyridoxal-5’-phosphate and characterized by using FT-IR, 1H NMR, and 13C NMR spectroscopic techniques. The resulting Schiff bases were utilized as bidentate ligands, coordinating via imine nitrogen and phenolate oxygen atoms, to stabilize palladium ions. Aryl substituents on imine nitrogen allowed for fine tuning of the stereoelectronic properties of the Schiff bases. The catalytic activity of the selected palladium complexes was investigated in the Suzuki cross-coupling reaction of a series of aryl halides with boronic acids in H2O/EtOH (1:1). Out of four complexes investigated in the cross-coupling reactions, Pd(L8)2, bearing a methoxy substituent on aryl imine, showed the highest activity at low catalyst loading. The scope of the reaction was also investigated with 26 samples.
- Neshat, Abdollah,Gholinejad, Mohammad,?zcan, Hafize,Khosravi, Faezeh,Mobarakeh, Ali Mousavizadeh,Zaim, ?mer
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- Organometallic polymer-functionalized Fe3O4 nanoparticles as a highly efficient and eco-friendly nanocatalyst for C–C bond formation
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A magnetically recoverable biopolymer-based nanocatalyst was prepared through the covalent immobilization of a chitosan-bound 2-hydroxynaphthaldehyde Pd complex on the surface of superparamagnetic nanoparticles. The nanocatalyst was characterized by FTIR, X-ray powder diffraction and scanning electron microscopy, revealing an average particle size of 70?nm. The catalyst shows high thermostability by thermogravimetric analysis. Estimated Pd loading by inductively coupled plasma atomic emission analysis was found to be 0.348?mmol?g?1. The nanocatalyst exhibits excellent catalytic performance in Suzuki couplings of various aryl halides with phenylboronic acid, and Heck reactions of iodo- and bromoarenes with butylacrylate. The catalyst can be easily separated from the reaction mixture with an external magnet and reused consecutively four times without significant loss in activity.
- Fakhri, Akram,Naghipour, Ali
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- Pd(0) complex of fuberidazole modified magnetic nanoparticles: A novel magnetically retrievable high-performance catalyst for Suzuki and Stille C-C coupling reactions
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Fuberidazole has been successfully immobilized onto nano-Fe3O4 supported (3-chloropropyl)trimethoxysilane (3-CPTS) leading to a novel functionalized magnetic nanoparticle (FB/MNP). The Pd(0) complex, Pd-FB/MNP, was prepared by grafting Pd (OAc)2 on FB/MNP and subsequent reduction of a synthesized Pd (II) complex using NaBH4. Pd-FB/MNP has been characterized by FT-IR, SEM, TGA, XRD, ICP, EDS, BET and VSM. The Pd(0) complex proved to be an efficient phosphine- and halide-free recyclable heterogeneous catalyst for Suzuki as well as for Stille C-C coupling reactions showing high catalytic activity (up to 98percent). Its catalytic activity in both reactions has been studied in PEG-400 as a green solvent. Besides, the selectivity of aryl iodide and aryl bromide over aryl chloride is observed during the C-C coupling reaction. The catalyst could be recovered easily from the reaction mixture using an external magnet device and recycled several times without considerable loss in activity. Additionally, the results of a palladium leaching test of the nano-catalyst demonstrate that no leaching of Pd took place during the C-C coupling process making the procedure environmentally friendly.
- Nouri, Kheirollah,Ghassemzadeh, Mitra,Mohsenzadeh, Farshid,Afsharpour, Maryam
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- Palladium-doped mixed oxides as 'slow-release' catalysts for suzuki couplings
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Palladium-containing sol-gel materials are efficient catalysts for Suzuki couplings. Especially good results are obtained under microwave irradiation in water. At least in this solvent, homogeneous palladium species are responsible for the catalytic activity. Georg Thieme Verlag Stuttgart.
- Kazmaier, Uli,H?hn, Saskia,Weiss, Torsten D.,Kautenburger, Ralf,Maier, Wilhelm F.
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- A thiosemicarbazone–palladium(II)–imidazole complex as an efficient pre-catalyst for Suzuki–Miyaura cross-coupling reactions at room temperature in aqueous media
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Abstract: A Pd(II) complex of two sterically crowded ligands, specifically an N,S-donor thiosemicarbazone and an N-donor imidazole, has been synthesized and characterized by physicochemical and spectroscopic methods. X-ray single-crystal analysis revealed that the coordination geometry around the palladium center is distorted square planar, and the chloride ligand is involved in intermolecular bifurcated X–HY-type (where X?=?C, N and Y?=?Cl) hydrogen bonding. This complex proved to be a highly active and retrievable pre-catalyst for additive-free Suzuki–Miyaura cross-coupling reactions of arylboronic acids with aryl bromides or chlorides at room temperature and 60?°C, respectively. The reactions require a low catalyst loading and the complex is converted to ~1.5–2.0 nm-sized Pd nanoparticles (probably the real catalyst). The catalyst can be reused up to seven times without significant loss in activity. Since the reaction proceeds under mild conditions in aqueous medium and the catalyst is recoverable, it provides an environmentally benign alternative to the existing protocols for Suzuki–Miyaura reactions. Graphical abstract: Biaryls can be synthesized in high yield under greener reaction conditions in the presence of efficient pre-catalyst, thiosemicarbazone–palladium(II)–imidazole.[Figure not available: see fulltext.].
- Baruah, Jayantajit,Gogoi, Rajjyoti,Gogoi, Nibedita,Borah, Geetika
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- Highly efficient phosphine-free Suzuki aryl couplings mediated by an in situ generated Pd(OAc)2/metformin complex in green media
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An in situ generated complex of palladium(II) and a biguanide, namely metformin, was found to be a highly efficient homogeneous catalyst for the phosphine-free Suzuki-Miyaura reaction. Significant rate acceleration of the palladium-catalyzed coupling was observed when a 1:1 mixture of ethanol/water was employed as the reaction solvent. Using this protocol, a variety of aryl halides (Cl, Br, I) were subjected to reaction with various arylboronic acids and the products were obtained in good to excellent yields under mild reaction conditions.
- Alizadeh,Khodaei,Kordestani,Beygzadeh
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- A simple, quick and novel protocol for biaryl synthesis using LiCl-promoted in situ-generated Pd nanoparticles
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This paper describes a simple and a very quick protocol for biaryl synthesis using the Suzuki–Miyaura cross-coupling reaction. A quintessential role of salting-out agent LiCl was observed in the Suzuki–Miyaura cross-coupling reaction that enhanced the red
- Phukan, Parmita,Boruah, Preeti Rekha,Gehlot, Praveen Singh,Kumar, Arvind,Sarma, Diganta
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- A one-pot efficient and fast Hiyama coupling using palladium nanoparticles in water under fluoride-free conditions
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An efficient Hiyama cross-coupling of a wide variety of substituted aryl bromides and iodides with arylsilanes has been achieved at 100 °C in water through a simple one-pot operation using in situ generated palladium nanoparticles. This reaction is very fast (5 min) and has been performed in air under fluoride-free conditions, giving excellent chemoselectivity and high yields.
- Ranu, Brindaban C.,Dey, Raju,Chattopadhyay, Kalicharan
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- Catalytic properties of palygorskite supported Ru and Pd for efficient oxidation of alcohols
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Natural palygorskite (PG) was employed to prepare cost-effective, reusable supported catalyst of Pd/PG and Ru/PG through wet impregnation method. The catalysts were characterized through AFM, ICP-AES, XPS, XRD, BET, TEM and FTIR. The catalytic properties of the synthesized catalysts were assessed and optimized through oxidation of alcohols with PhIO as oxidant. It showed that the existence of Ru and Pd in the catalysts dramatically enhanced the catalytic activity with a prominent selectivity of far more than 99% compared with the palygorskite.
- Yang, Zhi-Wang,Zhao, Xia,Li, Tian-Jing,Chen, Wen-Long,Kang, Qiao-Xiang,Xu, Xue-Qing,Liang, Xi-Xi,Feng, Ying,Duan, Huan-Huan,Lei, Zi-Qiang
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- Biguanide/Pd(OAc)2 immobilized on magnetic nanoparticle as a recyclable catalyst for the heterogeneous Suzuki reaction in aqueous media
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Immobilization of Pd(II) ions on magnetite nanoparticle (MNP) has been simply achieved through a surface modification of Fe3O4 nanoparticle with a biguanide. This surface-modified nanoparticle was characterized by various techniques such as TEM, XRD, VSM, TGA, elemental analyzer, atomic absorption spectroscopy, N2 adsorption-desorption (BET and BJH), and FT-IR. This nanosolid exhibits excellent catalytic activity for heterogeneous Suzuki reaction in aqueous media, and could be easily separated by an external magnet and reused for several times. TEM study of the recovered catalyst showed the preservation of the support core-shell structure and the good dispersion of the produced palladium nanoparticles.
- Beygzadeh,Alizadeh,Khodaei,Kordestani
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- Application of Pd-2A3HP-MCM-41 to the Suzuki, Heck and Stille coupling reactions and synthesis of 5-substituted 1H-tetrazoles
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An ecofriendly heterogeneous catalyst has been synthesized by anchoring palladium onto the surface of organically modified mesoporous silica. The prepared catalyst was characterized using X-ray diffraction, Fourier transform infrared and energy-dispersive X-ray spectroscopies, transmission and scanning electron microscopies, inductively coupled plasma and thermogravimetric techniques. The catalyst shows high activity in the Suzuki, Heck and Stille cross-coupling reactions and the synthesis of 5-substituted 1H-tetrazoles from sodium azide (NaN3). These methods have the advantages of high yields, green reaction conditions, simple methodology and easy separation and workup.
- Nikoorazm, Mohsen,Ghorbani-Choghamarani, Arash,Khanmoradi, Maryam
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- Solid sheet of anodic aluminium oxide supported palladium catalyst for Suzuki coupling reactions
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A Pd(II) Schiff base complex supported on anodic aluminium oxide (with Al substrate sheet) was successfully prepared. The prepared nanocatalyst was characterized by SEM, TEM and XPS. The synthesized Pd-based catalyst showed excellent catalytic activity for Suzuki cross-coupling reactions under mild conditions. The catalytic activity did not deteriorate after five repeated cycles. Pd(II) Schiff base complex supported on solid sheets could be separated and recovered easily by taking it out of the reaction solution. The construction of solid sheet supported Pd catalyst would be expected to be a promising system to perform heterogeneous catalytic reactions.
- Nong, YongLing,Qiao, NiNa,Deng, TianHui,Pan, ZiNi,Liang, Ying
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- Pillar[5]arene-Based Organometallic Cross-Linked Polymer: Synthesis, Structure Characterization, and Catalytic Activity in the Suzuki-Miyaura Coupling Reaction
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Heterogeneous catalysts, as an emerging research hotspot, have showed excellent advantages on stability, recyclability, and separation from reactant compared with homogeneous catalysts in recent years. Herein, pillar[5]arene-based organometallic cross-linked polymer (P[5]-OCP) was constructed via the complexation between imidazolium-derivatived pillar[5]arene (P[5]) and Pd(OAc)2. The chemical compositions and structure of the P[5]-OCP were confirmed by means of multiple characterization methods. The catalytic activity and process of P[5]-OCP were emphatically investigated in the Suzuki-Miyaura coupling reaction. The P[5]-OCP showed outstanding catalytic activity in mild reaction conditions. Meanwhile, the catalyst P[5]-OCP possessed excellent stability and recyclability, which could be reused at least five times without significant loss of activity. Furthermore, the P[5]-OCP is easily synthesized and cost-effective, which make it a candidate for applications in fine chemical engineering. [Figure Presented]
- Liu, Yuezhou,Lou, Baohui,Shangguan, Liqing,Cai, Jingsong,Zhu, Huangtianzhi,Shi, Bingbing
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- Palladium nanoparticles-anchored dual-responsive SBA-15-PNIPAM/PMAA nanoreactor: A novel heterogeneous catalyst for a green Suzuki-Miyaura cross-coupling reaction
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To develop a sustainable and cost-effective catalyst for cross-coupling reactions, dual (temperature and pH)-responsive poly(N-isopropyl acrylamide-co-methacrylic acid) (PNIPAM/PMAA) functionalised SBA-15 was synthesised via free radical polymerisation using potassium persulfate as an initiator and decorated with palladium nanoparticles (PdNPs-SBA-15-PNIPAM/PMAA). The X-ray photoelectron spectroscopic analysis revealed that the Pd content in the zero oxidation state of the catalyst was 1.21 wt%. The dynamic light scattering studies showed that the catalyst exhibited swelling behaviours at low temperatures (4), but exhibited deswelling behaviours at high temperatures (>32 °C) and low pH (90%) were realized for the room-temperature SMC reaction in an aqueous medium for various substituted aryl halides, while the conversion was low at relatively high temperatures (>32 °C). The conversion was dependent on the different electronic effects between the electron-releasing and electron-withdrawing groups of the aryl halides. After the experiment, the catalyst was successfully recovered without any loss of heterogeneity and could be reused at least up to the fifth cycle. This journal is
- Ha, Chang-Sik,Mohan, Anandhu,Nagappan, Saravanan,Parambadath, Surendran,Peter, Jerome,Rout, Lipeeka,Thomas, Anju Maria
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- Simple amine/Pd(OAc)2-catalyzed Suzuki coupling reactions of aryl bromides under mild aerobic conditions
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A new palladium catalyst (DAPCy) made from Pd(OAc)2 and commercially available, inexpensive dicyclohexylamine has been developed for the Suzuki coupling reaction of aryl bromides with boronic acids to give the coupling products in good to high yields. The air-stable catalyst was characterized and well-defined by X-ray crystallography. A catalytic system involving DAPCy in dioxane demonstrates a temperature-dependent reactivity toward aryl bromides with different electronic substituents, and selectively couples electron-deficient aryl bromides with boronic acids over electron-rich ones at room temperature. Another catalytic system employing DAPCy in EtOH provides a general and convenient method to prepare biaryls from aryl bromides and boronic acids with a broad range of functional groups at room temperature and under aerobic conditions.
- Tao, Bin,Boykin, David W.
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- Green synthesis of carbon quantum dots from vanillin for modification of magnetite nanoparticles and formation of palladium nanoparticles: Efficient catalyst for Suzuki reaction
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In this report we prepared carbon quantum dots (CQD) from vanillin as an ecofriendly and naturally abundant compound for modification of magnetic nanoparticles (CQD@Fe3O4 NPs). This new magnetic solid has been used for complete reduction of PdCl2 with formation of stabilized palladium nanoparticles (Pd@CQD@Fe3O4 NPs) and characterized by SEM, TEM, EDX, solid UV, VSM, XPS, XRD, and N2 adsorption–desorption analyses. These magnetic supported Pd NPs have been used as an efficient catalyst for the Suzuki-Miyaura cross-coupling reactions of aryl bromides at room temperature in aqueous ethanol and of aryl chlorides at 120 °C in PEG200 under low catalyst loading in air. The heterogeneous catalyst can be easily recovered by an external magnet and reused for eight consecutive runs.
- Gholinejad, Mohammad,Najera, Carmen,Hamed, Fatemeh,Seyedhamzeh, Mohammad,Bahrami, Maede,Kompany-Zareh, Mohsen
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- Schiff-based Pd(II)/Fe(III) bimetallic self-assembly monolayer—preparation, structure, catalytic dynamic and synergistic
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Graphene oxide supported Pd (II)/Fe (III) bimetallic catalytic monolayer (denoted as GO@H-Pd/Fe) was prepared and characterized. Its catalytic performances for Suzuki coupling reaction, synergetic effect and catalytic mechanism were systematic investigated. Results showed that orientation, composition and distribution of catalyst had efficient effect on catalytic activity. Catalytic activity of GO@H-Pd0.10/Fe0.90 was 475 times more than that of GO@H-Pd due to the ordered catalytic monolayer immobilized on GO, proper ratio of Pd/Fe and the synergetic effect between Pd(II) and Fe(III) which could form active cluster containing Pd and Fe. The Pd(II) could be made more negative by transferring electron from GO to Fe(III) via ligand and then to Pd, improving its catalytic activity since it was easy for oxide addition. It also exhibited better stability and recyclability at least 8 times due to proper functional ligand and support. Deactivation mechanism was confirmed to be the aggregation of active centre during the recycling. Heterogeneous catalytic mechanism was also proved by poison test, hot filtration and ReactIR. The results of ReactIR presented different dynamic catalytic process for GO@H-Pd0.10Fe0.90 and homogeneous catalyst (Li2PdCl4/FeCl3·6H2O).The activation energies were 9.7 KJ/mol and 3.7 KJ/mol obtained for heterogeneous and homogeneous catalyst, respectively. Considering the diffusion effect, the factor of supports on the activity was also investigated by ReactIR, with which that GO@H-Pd0.10Fe0.90 catalytic activity was higher than that of homogeneous catalyst could be confirmed.
- Huang, Pingping,Song, Erran,Sun, Yimeng,Li, Tiesheng,Wei, Donghui,Liu, Minghua,Wu, Yangjie
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- Organic/inorganic salting-in/salting-out agents as promoters of Pd-catalysed ligand free synthesis of biaryls in water
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Biaryls were synthesized using Pd-catalyzed Suzuki-Miyaura cross coupling reactions of aryl halides with aryl boronic acids in water in the presence of organic/inorganic additives as promoters. The coupling reactions, carried out in absence of ligand, proceed in good to excellent yields with easy product isolation and in relatively shorter reaction time.
- Boruah, Preeti Rekha,Bora, Sankar Jyoti,Saikia, Prakash J.,Sarma, Diganta
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- S-Benzylisothiourea complex of palladium on magnetic nanoparticles: A highly efficient and reusable nanocatalyst for synthesis of polyhydroquinolines and Suzuki reaction
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S-Benzylisothiourea complex of palladium supported on modified Fe3O4 magnetic nanoparticles (Pd-SBTU@Fe3O4) is reported for carbon–carbon coupling through the Suzuki coupling reaction. Also, the synthesis of pol
- Ghorbani-Choghamarani, Arash,Tahmasbi, Bahman,Moradi, Zahra
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- Palladium Nanoparticles Supported on Zirconium Metal Organic Framework as an Efficient Heterogeneous Catalyst for the Suzuki-Miyaura Coupling Reaction
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Nanoparticles of zirconium metal organic framework UiO-66 (about 100 nm) have been used as proper supports for Pd nanoparticles. Highly dispersed Pd nanoparticles (about 3-15 nm) were deposed on activated UiO-66 metal organic framework using simple wet impregnation method at room temperature. UiO-66 and the supported Pd nanoparticles (Pd/UiO-66) were characterized by X-ray diffraction, N2 sorption, field emission scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and inductively coupled plasma atomic emission spectroscopy. Investigation of the catalytic performance of Pd/UiO-66 showed that the synthetic nanocomposites can effectively catalyze the Suzuki-Miyaura cross-coupling reaction of benzeneboronic acid with different aryl halides under mild reaction conditions using environmentally benign solvents. In addition, the stability and reusability of the catalyst were studied during the catalytic reaction and it is worth noting that the structure of Pd/UiO-66 catalyst remains intact during the catalytic reaction and the catalyst can be recycled four times without significant decrease in its catalytic activity.
- Pourkhosravani,Dehghanpour,Farzaneh
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- Thiourea bridged periodic mesoporous organosilica with ultra-small Pd nanoparticles for coupling reactions
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A synthesis of thiourea-bridged mesoporous organosilica is reported. Using transmission electron microscopy, low-angle XRD measurements and N2 adsorption-desorption isotherms the formation of a highly ordered mesoporous structure with a high surface area (>400 m2 g-1) has been confirmed. Deposition of Pd nanoparticles inside the mesopores resulted in a material that showed excellent catalytic activity in a Suzuki-coupling reaction and retained this activity over several consecutive runs.
- Doustkhah, Esmail,Rostamnia, Sadegh,Imura, Masataka,Ide, Yusuke,Mohammadi, Shiva,Hyland, Christopher J. T.,You, Jungmok,Tsunoji, Nao,Zeynizadeh, Behzad,Yamauchi, Yusuke
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- A novel water-soluble NHC-Pd polymer: An efficient and recyclable catalyst for the Suzuki coupling of aryl chlorides in water at room temperature
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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.
- Karimi, Babak,Fadavi Akhavan, Pari
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- A new recyclable/reusable ionic liquid/LiCl system for Suzuki-Miyaura cross coupling reactions
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Suzuki-Miyaura cross coupling reactions of aryl halides with aryl boronic acids were carried out in basic ionic liquids in the presence of lithium chloride as a promoter. The coupling reactions, carried out in the absence of base and ligand, proceed in good to excellent yields with easy product isolation and catalyst recycle.
- Boruah, Preeti Rekha,Koiri, Milon J.,Bora, Utpal,Sarma, Diganta
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- 1-Butyl-3-methyl-2-(diphenylphosphino)imidazalolium hexafluorophosphate as an efficient ligand for recoverable palladium-catalyzed Suzuki-Miyaura reaction in neat water
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The 1-butyl-3-methyl-2-(diphenylphosphino)imidazalolium hexafluorophosphate is prepared and used as a water-soluble ligand in the Suzuki-Miyaura reaction. This ligand and palladium chloride generates a new active catalyst for the Suzuki coupling reaction between aryl iodides or bromides with arylboronic acids in neat water. This catalyst can be recycled and reused for the coupling reaction of 4-bromobenzonitrile with phenylboronic acid for at least six runs with low decreasing in catalytic activity.
- Khosravi, Faezeh,Gholinejad, Mohammad,Lledó, David,Grindlay, Guillermo,Nájera, Carmen,Sansano, José M.
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- Pd embedded N, S co-doped graphene wrapped core-shell magnetic nanospheres: Engineered stable nanocatalyst for Suzuki couplings
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Designed nitrogen and sulfur co-doped graphene wrapped magnetic core-shell supported Pd nanoparticles were synthesized through the following steps. Firstly, Fe3O4 was prepared, coated with silica and then functionalized with amine groups to create a positive charge on the structure for enhancing the interaction of the Fe3O4@SiO2 with graphene oxide. Secondary, the pre-catalyst wrapped with graphene to enhance adsorption of aromatic substrates through π–π stacking. Thirdly, graphene was doped with nitrogen and sulfur to increase the grafting of Pd in hybrid. Finally, Pd NPs were attached on the surface of pre-engineered structure to produce Fe3O4@SiO2@N,S-wG@Pd which exhibited high performance in Suzuki reactions. This superior activity can be indexed to the incorporation of N and S atoms into graphene led to high anchoring and well-dispersion of Pd NPs on the nanocomposite surface offering large amounts of active centers, that strongly increased the interaction between Pd and substrates to decreases Pd leaching.
- Rohani, Sahar,Mohammadi Ziarani, Ghodsi,Badiei, Alireza
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- Palladium supported on modified magnetic nanoparticles: A phosphine-free and heterogeneous catalyst for Suzuki and Stille reactions
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An efficient magnetic nanoparticle-supported palladium (Fe3O4/SiO2-PAP-Pd) catalyst is reported for the Suzuki cross-coupling and Stille reactions. This method provides a novel and much improved modification of the Suzuki and Stille coupling reactions in terms of phosphine-free catalyst, short reaction time, clean reaction and small quantity of catalyst. Another important feature of this method is that the catalyst can be easily recovered from the reaction mixture and reused with no loss of its catalytic activity.
- Ghorbani-Choghamarani, Arash,Norouzi, Masoomeh
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- Ni2O3-around-Pd hybrid on graphene oxide: An efficient catalyst for ligand-free Suzuki-Miyaura coupling reaction
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Ni2O3-around-Pd hybrid can be fabricated on graphene oxide (Pd-Ni/RGO) by a simple one-pot wet chemical route. These isolated Pd clusters showed significantly improved performance for Suzuki coupling reaction compared to that of pure Pd/RGO, Ni2O3/RGO, popularly reported Pd/AC, as well as homogeneous PdCl2 and PdCl 2(PPh3)2. Characterizations disclosed that Ni2O3 plays multiple roles in exfoliating graphene sheets, mediating the size as well as stability of Pd clusters. Pd-Ni/RGO dispersed homogeneously in the aqueous reaction mixture, exhibited high enrichment towards reactants as well as extremely high activity and stability for the Suzuki coupling reaction. The best turnover frequencies of all Pd atoms reached 38,750 h-1 at 80 C for bromobenzene coupling. It was concluded that the intimate interaction between Ni2O3 nanoparticles and Pd clusters appears to be beneficial for activating the Pd surface for the catalytic cycle.
- Nie, Renfeng,Shi, Juanjuan,Du, Weichen,Hou, Zhaoyin
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- Tris(4-methylpiperazin-1-yl)phosphane, P(NC4H 8NMe)3: Synthesis, structural studies, group 10 and 11 metal complexes and catalytic investigations
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Group 10 and 11 metal complexes of a multidentate phosphorus-nitrogen donor ligand tris(4-methylpiperazin-1-yl)-phosphane, P(NC4H 8NMe)3 (1) are reported. The reactions of 1 with an equimolar amount of CuX (X = Cl, Br and I) afford tetranuclear cubane-like complexes [(CuX)-{P(NC4H8NMe)3}]4 (2, X = Cl; 3, X = Br and 4, X = I) in excellent yield. Treatment of 1 with AuCl(SMe2) produces a mononuclear complex, [(AuCl){P(NC 4H8NMe)3}] (5). Reaction of 1 with AgCN produces a 2D AgI polymeric sheet, [(AgCN)2-{P(NC4H 8NMe)3}]n (6) in moderate yield. The similar 1:1 reactions of 1 with AgX (X = Cl and Br) furnish dinuclear complexes, [(AgX){P(NC4H8NMe)3}]2 (7, X = Cl and 8, X = Br). The 2:1 reactions of 1 with [M(COD)Cl2] (M = Pd or Pt) afford [{P(NC4H8NMe)3}2MCl 2] (9, M = Pd and 10, M = Pt) in quantitative yield. The molecular structures of complexes 1-3 and 6 are established through single-crystal X-ray diffraction studies. The catalytic activity of the PdII complex 9 has been investigated in Suzuki cross coupling reactions. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Ganesamoorthy, Chelladurai,Mague, Joel T.,Balakrishna, Maravanji S.
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- Salicylaldoxime-functionalized poly(ethylene glycol)-bridged dicationic ionic liquid ([salox-PEG1000-DIL][BF4]) as a novel ligand for palladium-catalyzed Suzuki-Miyaura reaction in water
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Two novel salicylaldoxime-functionalized poly(ethylene glycol)-bridged dicationic ionic liquids ([salox-PEG1000-DIL][BF4] and [salox-PEG1000-DIL][PF6]) were prepared and characterized. [salox-PEG1000-DIL][BF4] was found to be an efficient and recyclable ligand for palladium-catalyzed Suzuki-Miyaura reaction in water. The catalytic system could be easily recovered and reused for at least five runs only with slight decrease in its activity. Copyright
- Wang, Yinglei,Luo, Jun,Liu, Zuliang
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- Air-stable Pd(II) catalysts with cryptand-22 ligand for convenient and?efficient Suzuki cross-coupling reactions
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Air-stable Pd(II) catalysts with cryptand-22 ligand was easily handled in atm air at room temperature for Suzuki cross-coupling reactions of aryl bromides with arylboronic acids both containing electron-withdrawing and electron-donating groups. Generally, reactions proceeded fast to completion in 2 h to give high product yields. Our Pd(OAc)2/cryptand-22 catalyst is unique, since the reaction solution remained yellow during reaction period and air-stable without formation of Pd black as usually observed for ordinary simple amine ligands.
- Hsu, Ming-Hui,Hsu, Chien-Ming,Wang, Ju-Chun,Sun, Chia-Hsing
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- Synthesis and Characterization of Pd Schiff Base Complex Immobilized onto Functionalized Nanoporous MCM-41 and its Catalytic Efficacy in the Suzuki, Heck and Stille Coupling Reactions
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Abstract: The present work describes the use of palladium-vanillin-Schiff-base complex immobilized on MCM-41 nanostructure as efficient catalyst for the Suzuki–Miyaura, Stille and Mizoroki–Heck reactions of several aryl halides under aerobic conditions. All the reactions were carried out in green solvents (H2O and PEG-400). The developed procedure results bring several benefits such as uses of inexpensive and non-toxic ligand (vanillin), easy catalyst/product separation and catalyst recycling. The catalyst can be reused at least for five consecutive cycles without a significant loss of its catalytic activity or metal leaching. Graphical Abstract: [Figure not available: see fulltext.].
- Khanmoradi, Maryam,Nikoorazm, Mohsen,Ghorbani-Choghamarani, Arash
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- Heterogeneous Fe3O4@chitosan-Schiff base Pd nanocatalyst: Fabrication, characterization and application as highly efficient and magnetically-recoverable catalyst for Suzuki-Miyaura and Heck-Mizoroki C-C coupling reactions
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An environmentally friendly palladium-based catalyst supported on magnetite nanoparticles was successfully prepared. FT-IR, XRD, VSM, SEM, EDS and TGA studies have been used to characterize the nanocatalyst. The catalytic activity of the as-prepared catalyst was evaluated as a heterogeneous catalyst for the Suzuki-Miyaura carbon-carbon cross-coupling reaction of aryl halides and phenylboronic acid. Furthermore, it was found that the catalyst showed a high activity for the Mizoroki-Heck reaction of aryl halides and n-butyl acrylate. Interestingly, the novel catalyst could be recovered in a facile manner from the reaction mixture and recycled consecutive five runs without any significant loss in activity.
- Naghipour,Fakhri
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- Magnetic nanoparticles supported oxime palladacycle as a highly efficient and separable catalyst for room temperature Suzuki-Miyaura coupling reaction in aqueous media
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A novel magnetic nanoparticle-supported oxime palladacycle catalyst was successfully prepared and characterized. The magnetically recoverable catalyst was evaluated in the room temperature Suzuki-Miyaura cross-coupling reaction of aryl iodides and bromides in aqueous media. The catalyst was shown to be highly active under phosphine-free and low Pd loading (0.3 mol%) conditions. The catalyst could be easily separated from the reaction mixture using an external magnet and reused for six consecutive runs without significant loss of activity.
- Gholinejad, Mohammad,Razeghi, Mehran,Najera, Carmen
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- Pd–ninhydrin immobilized on magnetic nanoparticles: synthesis, characterization, and application as a highly efficient and recoverable catalyst for Suzuki–Miyaura and Heck–Mizoroki C–C coupling reactions
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Abstract: In this work by controlling the interaction between the inorganic complexes and the support material, we have designed a high-activity nanostructured combined of magnetic nanoparticles and Pd–ninhydrin-terminated complex as catalyst. The as-prepared catalyst was characterized by FT-IR, XRD, VSM, SEM, EDAX, ICP, and TGA techniques. This magnetic nanostructure can be used as a novel, green, and efficient heterogeneous catalyst for Suzuki–Miyaura and Heck–Mizoroki C–C coupling reactions. This catalyst showed promising catalytic activity and excellent yields toward various aryliodides and arylbromides in mild reaction conditions. In Suzuki–Miyaura reactions, various aryl halides (I, Br) were coupled with phenyl boronic acids in 5?mg of catalyst and 8?mg of catalyst used for Mizoroki–Heck reaction of aryl halides (I, Br) with n-butyl acrylate or acrylonitrile. The catalyst was reusable and recycled six times without a significant loss in activity and leaching of palladium. Graphic abstract: [Figure not available: see fulltext.].
- Hajjami, Maryam,Shirvandi, Zeinab
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- Facile construction & modeling of a highly active thiacalixphenyl[4]arene-protected nano-palladium catalyst for various C-C cross-coupling reactions
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The design and creation of thiacalixphenyl[4]arene tetraacetohydrazide (TPTAH) has been utilized for the construction of palladium nanoparticles (PdNps). The molecular modelling studies give an insight into the surface properties of TPTAH capped PdNps. The plausible reduction mechanism of Pd(ii) to Pd(0) is due to the presence of hydrazide group on the periphery. The charge transfer for this reduction was initiated by the carbonyl group and N-atom. TPTAH behaves as a reducing and stabilizing agent for the formation of catalytically active TPTAH-PdNps that were characterized by UV-Vis spectroscopy, selected area electron diffraction (SAED), transmission electron microscopy (TEM), and powder X-ray diffraction. The TPTAH-PdNps with size 4 ± 2 nm were found to be catalytically active for C-C cross-coupling reactions such as the Suzuki-Miyaura, Heck, and Stille reactions. TPTAH-PdNps are superior to the conventional Pd catalyst in terms of yield, catalyst loading, reaction time, and recyclability.
- Modi, Krunal,Patel, Chirag,Panchal, Urvi,Liska, Alan,Kongor, Anita,Jiri, Ludvik,Jain
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- Proximity Effect using a Nanocage Structure: Polyhedral Oligomeric Silsesquioxane-Imidazolium Tetrachloro- palladate Salt as a Precatalyst for the Suzuki-Miyaura Reaction in Water
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A polyhedral oligomeric silsesquioxane-imidazolium tetrachloropalladate salt (POSS-Imi-PdCl4) was prepared by the reaction of a polyhedral oligomeric silsesquioxane-imidazolium chloride salt (POSS-Imi-Cl) with PdCl2 and used as a pre-catalyst for the Suzuki-Miyaura reaction in water at 100 °C at a low loading (0.08-0.16 mol %). Biphenyl compounds were isolated in high to excellent yields. A comparison of the POSS-based catalyst with the corresponding catalyst without the nanocage structure (i.e., 1-butyl-3-methylimidazolium tetrachloropalladate) highlighted the role of the POSS structure to reach higher yields in the Suzuki-Miyaura reaction. This result is ascribed to a proximity effect of the imidazolium moieties linked to the nanocage structure. Fresh and used catalytic materials were characterised by using X-ray photoelectron spectroscopy and TEM.
- Bivona, Lucia Anna,Giacalone, Francesco,Carbonell, Esther,Gruttadauria, Michelangelo,Aprile, Carmela
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- New Palladium – ZrO2 Nano-Architectures from Thermal Transformation of UiO-66-NH2 for Carbonylative Suzuki and Hydrogenation Reactions
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The new nanocomposites, Pd/C/ZrO2, PdO/ZrO2, and Pd/PdO/ZrO2, were prepared by thermal conversion of Pd@UiO-66-Zr?NH2 (MOF) in nitrogen or air atmosphere. The presence of Pd nanoparticles, uniformly distributed on the ZrO2 or C/ZrO2 matrix, was evidenced by transmission electron microscopy, scanning electron microscopy (SEM), Raman and X-ray Photoelectron Spectroscopy (XPS) methods. All pyrolysed composites retained the shape of the MOF template. They catalyze carbonylative Suzuki coupling under 1 atm CO with an efficiency significantly higher than the original Pd@UiO-66-Zr?NH2. The most active PdO/ZrO2 composite, formed benzophenone with TOF up to 1600 h?1, while by using Pd@UiO-66-Zr?NH2, much lower TOF values, 51–95 h?1, were achieved. After the reaction, PdO/ZrO2 was recovered with the same composition and catalytic activity. Very good results were also obtained in the transfer hydrogenation of benzophenones to alcohols with Pd/C/ZrO2 and PdO/ZrO2 catalysts under microwave irradiation.
- Alsalahi, Waleed,Augustyniak, Adam W.,Tylus, W?odzimierz,Trzeciak, Anna M.
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supporting information
(2021/12/22)
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- Preparation of a magnetic and recyclable superparamagnetic silica support with a boronic acid group for immobilizing Pd catalysts and its applications in Suzuki reactions
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Palladium is one of the best metal catalysts for Suzuki cross-coupling reaction to synthesize unsymmetrical biaryl compounds. However, homogeneous palladium (Pd) is limited in an industrial scale due to the high cost, separation, removal, and recovery issues. In this paper, a novel, high activity magnetic nanoparticles (Fe3O4@SiO2-APBA-Pd) catalyst was prepared by a simple, cost-effective procedure. The as-prepared functional nanoparticles (Fe3O4@SiO2-APBA) with boric acid group immobilized Pd through adding Pd(OAc)2 to Fe3O4@SiO2-APBA in absolute ethanol and maintaining for a certain time under a nitrogen atmosphere. The as-prepared catalyst was characterized by FT-IR, SEM, EDX, TEM, ICP-MS, XPS, and XRD. The results showed that the Pd (0.2-0.6 nm) was successfully anchored on the magnetic silica material with boric acid group. The amount of Pd was 0.800 mmol g-1. This magnetic nanostructure (8-15 nm) is especially beneficial as a nanocatalyst because each nanoparticle can catalyze a reaction in a certain time without steric restriction, which could effectively improve the reaction efficiency. The current nanoparticles with the Pd catalyst could be used as a novel, green, and efficient heterogeneous catalyst for Suzuki reactions. This catalyst showed promising catalytic activity and excellent yields toward 14 kinds of Suzuki coupling reactions under mild reaction conditions, which was similar to homogeneous Pd and many reported heterogeneous Pd catalysts. In addition, the turnover number (TON) and turnover frequency (TOF) for the Suzuki reaction were high. TOF and TON were 9048 h-1 and 20?250 for the Suzuki reaction of bromobenzene and phenylboronic acid. Furthermore, the nanoparticles could be easily separated by a magnet, and could be used repeatedly seven times without any significant loss in activity.
- Aschenaki, Assefa,Bao, James Jianmin,Jia, Wenhui,Li, Youxin,Liu, Jia,Ren, Fangfang,Song, Qianyi,Zheng, Wenqing
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p. 33692 - 33702
(2021/12/07)
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- 3,3'-((Arylmethylene)bis(4-methoxy-3,1-phenylene)) dipyridine derivatives as convenient ligands for Suzuki–Miyaura chemo- and homoselective cross-coupling reactions
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Four novel N,N-bidentate triarylmethane-based ligands bearing β-pyridyl residues have been prepared and the catalytic activity of their in-situ generated palladium complexes were studied in the Suzuki–Miyaura cross-coupling reactions. Air and moisture stable 3,3'-((arylmethylene)bis(4-methoxy-3,1-phenylene))dipyridines L1-3 showed excellent activity in the Suzuki coupling reactions of aryl halides with aryl boronic acids under thermal and sonochemical reaction conditions. The described methodology provided good to high yields in short reaction times at ambient conditions. Moreover, it offered a straightforward way for Suzuki–Miyaura chemo- and homoselective cross-coupling of aryl halides with phenyl boronic acid. The structures of synthesized compounds were fully characterized by FT-IR, 1H-NMR, 13C-NMR, and elemental analyses. The coordination of palladium acetate to nitrogen sites of L1 was also studied using FTIR spectroscopy, EDX analysis and SEM observations. Graphic abstract: The in-situ generated Pd-complexes of N,N-bidentate ligands L1-3 are described as robust and highly effective catalytic systems for the Suzuki cross-coupling of aryl halides with aryl boronic acids under thermal and sonochemical reaction conditions.[Figure not available: see fulltext.]
- Hosseini, Raziyeh,Mohammadiannejad, Kazem,Ranjbar-Karimi, Reza
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- Potent Inhibition of Nicotinamide N-Methyltransferase by Alkene-Linked Bisubstrate Mimics Bearing Electron Deficient Aromatics
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Nicotinamide N-methyltransferase (NNMT) methylates nicotinamide (vitamin B3) to generate 1-methylnicotinamide (MNA). NNMT overexpression has been linked to a variety of diseases, most prominently human cancers, indicating its potential as a therapeutic target. The development of small-molecule NNMT inhibitors has gained interest in recent years, with the most potent inhibitors sharing structural features based on elements of the nicotinamide substrate and the S-adenosyl-l-methionine (SAM) cofactor. We here report the development of new bisubstrate inhibitors that include electron-deficient aromatic groups to mimic the nicotinamide moiety. In addition, a trans-alkene linker was found to be optimal for connecting the substrate and cofactor mimics in these inhibitors. The most potent NNMT inhibitor identified exhibits an IC50 value of 3.7 nM, placing it among the most active NNMT inhibitors reported to date. Complementary analytical techniques, modeling studies, and cell-based assays provide insights into the binding mode, affinity, and selectivity of these inhibitors.
- Buijs, Ned,Campagna, Roberto,Emanuelli, Monica,Gao, Yongzhi,Gutiérrez-De-Terán, Hugo,Innocenti, Paolo,Jespers, Willem,Martin, Nathaniel I.,Parsons, Richard B.,Sartini, Davide,Van Haren, Matthijs J.,Van Westen, Gerard J. P.,Zhang, Yurui
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p. 12938 - 12963
(2021/09/11)
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- Synthesis of Enaminone-Pd(II) Complexes and Their Application in Catalysing Aqueous Suzuki-Miyaura Cross Coupling Reaction
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A series of Pd(II)-enaminone complexes, termed Pd(eao)2, have been synthesized and characterized. The investigation on the catalytic activities of these new Pd(II)-reagents has proved that the Pd(eao)2-1 possesses excellent catalytic activity for the Suzuki- Miyaura cross coupling reactions of aryl bromides/chlorides with aryl/vinyl boronic acids in the environmentally benign media of aqueous PEG400 at low loading (5 mol‰). The superiority of this Pd(II)-reagent to those commercial Pd(II) and Pd(0) catalysts in catalyzing the reactions has been confirmed by parallel experiments. What's more, Pd(eao)2-2 has been found as a practical catalyst for the homo-coupling reactions of aryl boronic acids.
- Fu, Leiqing,Cao, Xiaoji,Wan, Jie-Ping,Liu, Yunyun
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p. 254 - 258
(2020/01/25)
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- Copper-Catalyzed Defluorinative Hydroarylation of Alkenes with Polyfluoroarenes
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A catalytic defluorinative hydroarylation of alkenes with polyfluoroarenes in the presence of dppbz-ligated Cu catalyst and silanes was developed. This method provides a straightforward and alternative avenue to synthetic important polyfluorinated arenes with readily available and bench-stable alkenes as latent nucleophiles, and therefore avoids conventional reliance on stoichiometric quantities of organometallic reagents. This reaction proceeds under very mild conditions and exhibits good functional group compatibility and high level of regioselectivity. The synthetic potential of this method was further demonstrated by a gram-scale synthesis, and an array of experimental studies were also carried out to elaborate the probable mechanism.
- Fu, Bin,Li, Xiaohong,Xiong, Tao,Yuan, Xiuping,Zhang, Qian,Zhang, Qiao
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supporting information
p. 23056 - 23060
(2020/10/19)
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- Monosubstituted, Anionic Imidazolyl Ligands from N?H NHC Precursors and Their Activity in Pd-Catalyzed Cross-Coupling Reactions
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We report that treatment of several 2-diphenylphosphinoimidazoles with Pd(II) salts generates monosubstituted N?H NHC?Pd complexes via insertion into the C?P bond. Removal of the N?H proton in situ leads to anionic (X-type) or imidazolyl-Pd complexes that are highly stable and catalytically active, achieving up to 340,000 turnovers at 1 ppm catalyst loading in Suzuki-Miyaura reactions. DFT-calculated Tolman electronic parameters for the sterically small ligands suggest that these ligands are significantly more donating than traditional NHCs, which provides a rationale for rapid cross-coupling catalysis. Excellent reactivity is also demonstrated in Sonogashira reactions. (Figure presented.).
- Clark, Kyle J.,Ess, Daniel H.,Jensen, Christopher A.,Kenney, Karissa C.,Larson, Alexandra J. S.,Martinez, Erin E.,Michaelis, David J.,Nazari, S. Hadi,Smith, Stacey J.,Valdivia-Berroeta, Gabriel A.
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supporting information
(2020/07/06)
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- L-lysine-Pd Complex Supported on Fe3O4 MNPs: a novel recoverable magnetic nanocatalyst for Suzuki C-C Cross-Coupling reaction
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In this work, L-lysine-Pd Complex, immobilized onto the surface of Fe3O4 MNPs, was successfully prepared via simple and inexpensive procedure. The prepared nanocatalyst was considered as a robust and clean nano-reactor catalyst for the Suzuki and Heck C-C Cross-Coupling reactions in water as the green condition. This eco-friendly heterogeneous catalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), X-Ray Diffractometer (XRD), energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma atomic emission spectroscopy (ICP), X-ray mapping, BET, thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) techniques. The use of a green medium, easy separation and workup, excellent reusability of the nanocatalyst and short reaction time are some outstanding advantages of this method.
- Ashraf, Muhammad Aqeel,Liu, Zhenling,Zhang, Dangquan,Alimoradi, Ashkan
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- Highly effective cellulose supported 2-aminopyridine palladium complex (Pd(II)-AMP-Cell?Al2O3) for Suzuki-Miyaura and Mizoroki–Heck cross-coupling
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In the present work, a novel, highly efficient, retrievable organo–inorganic hybrid heterogeneous catalyst (Pd(II)-AMP-Cell?Al2O3) has been prepared by covalent grafting of 2-aminopyridine on chloropropyl modified cellulose-alumina composite followed by complexation with palladium acetate. The catalyst was characterized by techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), inductive coupled plasma-atomic emission spectroscopy (ICP-AES) and thermo gravimetric analysis (TGA). The catalyst has been successfully employed in Suzuki-Miyaura as well as Mizoroki–Heck cross-coupling reactions. The reactions proceed smoothly resulting in the high yields of cross-coupling products (81 to 95%) within short reaction times. The catalyst can be efficiently recovered by simple filtration and reused for multiple cycles without considerable loss in the catalytic activity. The key-features of the present protocol include mild reaction conditions, simple work-up procedure, high stability of the catalyst, high turnover number (TON) and frequency (TOF), ease recovery and reusability of the catalyst.
- Mhaldar, Pradeep,Pore, Dattaprasad,Rashinkar, Gajanan,Vibhute, Sandip
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- Discovery of novel “Dual-site” binding oseltamivir derivatives as potent influenza virus neuraminidase inhibitors
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From our research group, it was noticed that oseltamivir derivatives targeting 150-cavity of neuraminidase enzyme (NA) could significantly increase antiviral activity. Thus, we further enriched the C5–NH2 position of oseltamivir structure to ob
- Ai, Wei,Cherukupalli, Srinivasulu,Ding, Xiao,Huang, Bing,Jia, Ruifang,Jiang, Xiangyi,Li, Zhong,Liu, Xinyong,Ma, Xiuli,Sun, Lin,Sun, Zhuosen,Wang, Defeng,Zalloum, Waleed A.,Zhan, Peng,Zhang, Jian
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- Microwave-assisted organic acid-base-co-catalyzed tandem Meinwald rearrangement and annulation of styrylepoxides
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A novel organic acid-base-co-catalyzed conversion of styrylepoxides into [1,1′-biaryl]-3-carbaldehydes was realized under microwave irradiation. Styrylepoxides first underwent an acid-catalyzed Meinwald rearrangement followed by a tandem base-catalyzed Michael addition, aldol addition, and aromatization sequence to generate [1,1′-biaryl]-3-carbaldehydes.
- Shi, Yi,Li, Siqi,Lu, Yang,Zhao, Zizhen,Li, Pingfan,Xu, Jiaxi
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p. 2131 - 2134
(2020/02/27)
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- Design, synthesis and biological evaluation of novel FFA1/GPR40 agonists: New breakthrough in an old scaffold
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Based on an old phenoxyacetic acid scaffold, CPU014 (compound 14) has been identified as a superior agonist by comprehensive exploration of structure-activity relationship. In vitro toxicity study suggested that CPU014 has lower risk of hepatotoxicity than TAK-875. During acute toxicity study (5–500 mg/kg), a favorable therapeutic window of CPU014 was observed by evaluation of plasma profiles and liver slices. Moreover, CPU014 promotes insulin secretion in a glucose-dependent manner, while no GLP-1 secretion has been enhanced. Other than good pharmacokinetic properties, CPU014 significantly improved glucose tolerance both in normal and diabetic models without the risk of hypoglycemia. These subversive findings provided a safer candidate CPU014, which is currently in preclinical study to assess its potential for the treatment of diabetes.
- Li,Liu, Chunxia,Yang, Jianyong,Zhou,Ye, Zhiwen,Feng,Yue, Na,Tong,Huang, Wenlong,Qian, Hai
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p. 608 - 622
(2019/07/05)
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- Pd–Schiff base complex supported on Fe3O4 magnetic nanoparticles: A new and highly efficient reusable catalyst for C–C bond formation in water
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A protocol is introduced for the preparation of a new cage-like Pd–Schiff base organometallic complex supported on Fe3O4 nanoparticles (Fe3O4@Schiff-base-Pd). The structure of the nanomagnetic catalyst was comprehensively characterized using Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy, Brunauer–Emmett–Teller measurements, scanning electron microscopy (SEM), transmission electron microscopy, X-ray mapping, thermogravimetric analysis, vibrating sample magnetometry and inductively coupled plasma atomic emission spectroscopy. In the second stage, the catalytic activity of this catalyst was studied in the Suzuki and Heck cross-coupling reactions in water as a green solvent. In this sense, simple preparation of the catalyst from commercially available materials, high catalytic activity, simple operation, short reaction times, high yields and use of green solvent are some advantages of this protocol. Finally, the nanocatalyst was easily recovered, using an external magnet, and reused several times without significant loss of its catalytic efficiency. In addition, the stability of the catalyst after recycling was confirmed using SEM, XRD and FT-IR techniques.
- Lei, Lei
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- Biochar as heterogeneous support for immobilization of Pd as efficient and reusable biocatalyst in C–C coupling reactions
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Biochar is a stable and carbon-rich solid which has a high density of carbonyl, hydroxyl and carboxylic acid functional groups on its surface. In this work, the surface of biochar nanoparticles (BNPs) was modified with 3-choloropropyltrimtoxysilane and further 2-(thiophen-2-yl)-1H-benzo[d]imidazole was anchored on its surface. Then, palladium nanoparticles were fabricated on the surface of the modified BNPs and further the catalytic application was studied as recyclable biocatalyst in carbon–carbon coupling reactions such as Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions. The structure of the catalyst was characterized using scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, thermogravimetric analysis, X-ray diffraction and atomic absorption spectroscopy. The catalyst can be reused several times without a decrease in its catalytic efficiency. In addition to the several advantages reported, application of biochar as catalyst support for the first time is a major novelty of the present work.
- Moradi, Parisa,Hajjami, Maryam,Valizadeh-Kakhki, Fatemeh
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- Magnetic MCM-41 nanoparticles as a support for the immobilization of a palladium organometallic catalyst and its application in C-C coupling reactions
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In this study, the surface of magnetic MCM-41 nanoparticles (MCM-41/Fe3O4) was modified by 3-Aminopropyltriethoxysilane (APTES) and further, 1-methyl imidazole was anchored on their surface using cyanuric chloride as a linker. Then, Pd2+ ions were immobilized on the surface of the modified MCM-41/Fe3O4 (Pd-imi-CC@MCM-41/Fe3O4), and its application was studied as a magnetically recyclable nanocatalyst in carbon-carbon coupling reactions between a wide range of aryl halides and butyl acrylate, methyl acrylate, acrylonitrile, phenylboronic acid, or 3,4-difluorophenylboronic acid under the conditions of a phosphine-free ligand and an air atmosphere. This catalyst has the advantages of both the Fe3O4 nanoparticles and mesoporous MCM-41. The structure of the catalyst was characterized via TEM, SEM, EDS, WDX, N2 adsorption-desorption isotherm, XRD, TGA, FT-IR, and AAS. Also, the recovered catalyst was characterized via SEM, AAS and FT-IR. All the products from the carbon-carbon coupling reaction were obtained with excellent yields and high TON and TOF values, which indicate the high efficiency and activity of this catalyst. The selectivity of this catalyst was studied with various aryl halides bearing different functional groups. Furthermore, the heterogeneity and stability of Pd-imi-CC@MCM-41/Fe3O4 was studied via AAS, and leaching and poisoning tests. According to the results, this heterogeneous catalyst can be reused several times.
- Tahmasbi, Bahman,Ghorbani-Choghamarani, Arash
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supporting information
p. 14485 - 14501
(2019/09/30)
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- Palladium decorated on a new dendritic complex with nitrogen ligation grafted to graphene oxide: Fabrication, characterization, and catalytic application
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Immobilized Pd nanoparticles on a new ligand, namely, tris(pentaethylene-pentamine)triazine supported on graphene oxide (Pdnp-TPEPTA(L)-GO) was introduced as a novel and robust heterogeneous catalyst for use in C-C bond formation reaction. The Pdnp-TPEPTA(L)-GO catalyst was synthesized by complexation of Pd with TPEPTA as a ligand with high N-ligation sites that were supported on graphene oxide through 3-chloropropyltrimethoxysilane. The prepared catalyst was characterized using some microscopic and spectroscopic techniques. The TPEPTA(L)-GO substrate is a 2D heterogeneous catalyst with a high specific surface area and a large amount of N-ligation sites. The Pdnp-TPEPTA(L)-GO catalyst used in the C-C bond formation reaction between aryl or heteroaryl and phenylboronic acid derivatives was applied towards the synthesis of biaryl units in high isolated yields. Notably, a series of competing experiments were performed to establish the selectivity trends of the presented method. Also, this catalyst system was reusable at least six times without a significant decrease in its catalytic activity.
- Golestanzadeh, Mohsen,Naeimi, Hossein
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p. 27560 - 27573
(2019/09/12)
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- Base-Free Suzuki–Miyaura Coupling Reaction Using Palladium(II) Supported Catalyst in Water
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Abstract: The carbon–carbon bond formation via Suzuki–Miyaura reaction was performed in water as green solvent. Pd(OAc)2(PPh3)2 supported on magnesium hydroxide and cerium carbonate hydroxide composite was prepared and characterized by various techniques. The cross-coupling reaction of aryl halides carried out in water using mild conditions. The effects of temperature, solvents, the amount of catalyst and leaving groups were studied to find the optimization conditions for cross-coupling reaction. Various aryl halides were smoothly transformed into the biaryls in good yields. In addition, the catalyst also exhibited stability and catalytic performance in the cross-coupling of aryl halides. Graphical Abstract: [Figure not available: see fulltext.] A new approach is developed for carbon–carbon bond formation via Suzuki–Miyaura reaction.2 Pd(OAc)2(PPh3)2?supported on mixed magnesium hydroxide and cerium carbonate hydroxide were prepared and characterized by XRD, XPS, SEM–EDX techniques. The cross-coupling reaction of aryl halides can be carried out in water and under mild conditions (80 °C).
- Tomar, Ravi,Singh, Nidhi,Kumar, Neeraj,Tomar, Vartika,Chandra, Ramesh
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- Nitro group reduction and Suzuki reaction catalysed by palladium supported on magnetic nanoparticles modified with carbon quantum dots generated from glycerol and urea
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Glycerol and urea were used as green and cheap sources of carbon quantum dots (CQD) for modifying Fe3O4 nanoparticles (NPs). The obtained CQD@Fe3O4 NPs were used for the stabilization of palladium species and the prepared catalyst, Pd@CQD@Fe3O4, was characterized using various techniques. This magnetic supported palladium was applied as an efficient catalyst for the reduction of aromatic nitro compounds to primary amines at room temperature using very low palladium loading (0.008?mol%) and also for the Suzuki–Miyaura cross-coupling reaction of aryl halides as well as challenging heteroaryl bromides and aryl diazonium salts with arylboronic acids and with potassium phenyltrifluoroborate. This magnetically recyclable catalyst was recovered and reused for seven consecutive runs in the reduction of 4-nitrotoluene to p-toluidine and for ten consecutive runs in the reaction of 4-iodoanisole with phenylboronic acid with small decrease of activity. The catalyst reused in the Suzuki reaction was characterized using transmission electron microscopy, vibrating sample magnetometry and X-ray photoelectron spectroscopy. Using experiments such as hot filtration and poisoning tests, it has been shown that the true catalyst works under homogeneous conditions according to the release–return pathway of active palladium species.
- Gholinejad, Mohammad,Zareh, Fatemeh,Nájera, Carmen
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- Denitrogenative palladium-catalyzed coupling of aryl halides with arylhydrazines under mild conditions
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The development of a method for the Pd(ii)-catalyzed denitrogenative coupling of arylhydrazines to give functionalized biaryls in good yield, using aryl bromides or aryl iodides as convenient and inexpensive aryl sources, is reported. High functional group tolerance is demonstrated for electronically distinct arylhydrazines as well as aryl halides. The desired products were isolated in good to excellent yields for 58 examples. Control experiments and mechanism studies revealed that the transformation undergoes a base-promoted Pd-catalyzed process.
- Chang, Sheng,Dong, Lin Lin,Song, Hai Qing,Feng, Bo
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supporting information
p. 3282 - 3288
(2018/05/15)
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- Method for preparing biaryl from aryl hydrazine and aryl bromide
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The invention discloses a method for preparing biaryl from aryl hydrazine and aryl bromide. The method comprises the following steps: under the action of a divalent palladium catalyst and a ligand, aryl hydrazine and aryl bromide are subjected to a denitrification coupling reaction in an organic solvent, and after the reaction is ended, the reaction product is subjected to aftertreatment to obtainthe biaryl. In the preparation method, cheap and easily available aryl bromide is used as an aryl source, and the reaction of aryl hydrazine and aryl bromide shows good functional group tolerance, and promotes the palladium catalytic process by alkali.
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Paragraph 0035; 0036; 0037; 0039
(2018/09/21)
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- Discovery of phenylsulfonyl acetic acid derivatives with improved efficacy and safety as potent free fatty acid receptor 1 agonists for the treatment of type 2 diabetes
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The free fatty acid receptor 1 (FFA1) has emerged as an attractive anti-diabetic target that mediates glucose-stimulated insulin secretion. Several FFA1 agonists have been reported, but many of them possessed somewhat high lipophilicity and/or molecular weight. Herein, we describe the identification of sulfone-carboxylic acid moiety with the multiple advantages of reducing lipophilicity, cytotoxicity and β-oxidation associated with compound 2. Further structure-activity relationship study based on the previleged scaffolds led to the discovery of 2-{(4-[(2’-chloro-[1,1’-biphenyl]-3-yl)methoxy]phenyl)sulfonyl}acetic acid (compound 20), which showed a better balance than compound 2 in terms of physicochemical properties, cytotoxicity profiles and pharmacokinetic properties. Subsequent in vivo studies demonstrated that compound 20 robustly improves the glucose tolerance both in normal and type 2 diabetic models without the risk of hypoglycemia. Compared to the high risk of TAK-875 induced liver toxicity, there was no significant adverse effects such as hepatic and renal toxicity were observed in the chronic toxicity studies of compound 20 even at the higher dose.
- Li, Zheng,Liu, Chunxia,Xu, Xue,Qiu, Qianqian,Su, Xin,Dai, Yuxuan,Yang, Jianyong,Li, Huilan,Shi, Wei,Liao, Chen,Pan, Miaobo,Huang, Wenlong,Qian, Hai
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p. 458 - 479
(2017/07/10)
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- Probing the Hydrophobic Binding Pocket of G-Protein-Coupled Lysophosphatidylserine Receptor GPR34/LPS1 by Docking-Aided Structure-Activity Analysis
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The ligands of certain G-protein-coupled receptors (GPCRs) have been identified as endogenous lipids, such as lysophosphatidylserine (LysoPS). Here, we analyzed the molecular basis of the structure-activity relationship of ligands of GPR34, one of the LysoPS receptor subtypes, focusing on recognition of the long-chain fatty acid moiety by the hydrophobic pocket. By introducing benzene ring(s) into the fatty acid moiety of 2-deoxy-LysoPS, we explored the binding site's preference for the hydrophobic shape. A tribenzene-containing fatty acid surrogate with modifications of the terminal aromatic moiety showed potent agonistic activity toward GPR34. Computational docking of these derivatives with a homology modeling/molecular dynamics-based virtual binding site of GPR34 indicated that a kink in the benzene-based lipid surrogates matches the L-shaped hydrophobic pocket of GPR34. A tetrabenzene-based lipid analogue bearing a bulky tert-butyl group at the 4-position of the terminal benzene ring exhibited potent GPR34 agonistic activity, validating the present hydrophobic binding pocket model.
- Sayama, Misa,Inoue, Asuka,Nakamura, Sho,Jung, Sejin,Ikubo, Masaya,Otani, Yuko,Uwamizu, Akiharu,Kishi, Takayuki,Makide, Kumiko,Aoki, Junken,Hirokawa, Takatsugu,Ohwada, Tomohiko
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supporting information
p. 6384 - 6399
(2017/08/02)
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- Fe3O4@Boehmite-NH2-CoII NPs: An inexpensive and highly efficient heterogeneous magnetic nanocatalyst for the Suzuki-Miyaura and Heck-Mizoroki cross-coupling reactions
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Herein we report the synthesis of a magnetically separable core-shell-like Fe3O4@Boehmite-NH2-CoII NPs as an environmentally friendly heterogeneous catalyst. The as-prepared nanocatalyst was well characterized by various techniques such as FT-IR, XRD, BET, TEM, FE-SEM, EDX, TGA, H2-TPR, VSM, ICP-OES and elemental analysis and evaluated for the Suzuki-Miyaura and Heck-Mizoroki cross-coupling reactions in a green solvent (H2O). The results of characterization studies revealed the superparamagnetic behavior of the Fe3O4 NP core encapsulated by a Boehmite NP shell. Also, it was clearly found that the size of the particles was about 13-54 nm. In comparison with previously reported catalysts, Fe3O4@Boehmite-NH2-CoII NPs exhibited perfect catalytic efficiency for the Suzuki-Miyaura and Heck-Mizoroki cross-coupling reactions under mild conditions without using toxic solvents. The concerted effects between individual components of the catalyst and also its unique egg-like nanostructure led to the high catalytic performance of Fe3O4@Boehmite-NH2-CoII NPs. Also, the introduction of Co significantly lowers the cost of the catalyst. More importantly, the longevity of the nanocatalyst was studied and it was found that the magnetic nanocatalyst was stable under the reaction conditions and could be easily reused for at least seven consecutive cycles without a discernible decrease in its catalytic activity or metal leaching.
- Mohammadinezhad, Arezou,Akhlaghinia, Batool
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p. 5625 - 5641
(2017/12/06)
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- An efficient and recoverable palladium organocatalyst for Suzuki reaction in aqueous media
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Meso-tetrakis[4-(methoxycarbonyl)phenyl]porphyrinatopalladium(II) as a palladium organocatalyst was synthesized and then used in aqueous media as a heterogeneous organocatalyst in Suzuki reaction. The prepared organocatalyst was characterized using UV–visible, infrared and NMR spectroscopies. It was found to be an efficient catalyst for Suzuki coupling reaction between phenylboronic acid and a broad range of aryl halides. Mild reaction conditions, water solvent as green media, and easy catalyst separation and reusability are the advantages of the presented method.
- Fareghi-Alamdari, Reza,Golestanzadeh, Mohsen,Bagheri, Omid
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- Aminophosphine Palladium(0) Complex Supported on ZrO2 Nanoparticles (ZrO2@AEPH2-PPh2-Pd(0)) as an Efficient Heterogeneous Catalyst for Suzuki–Miyaura and Heck–Mizoroki Reactions in Green Media
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Abstract: A new aminophosphine palladium(0) complex supported on ZrO2nanoparticles (ZrO2@AEPH2-PPh2-Pd(0)) was successfully synthesized and characterized using FT-IR, XRD, XPS, SEM, TEM, EDS, TGA and ICP techniques. Characterization results revealed that the synthesized catalyst had tetragonal and monoclinic structure with spherical morphology. The prepared nanocatalyst was showed excellent reactivity in the Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions. Moreover, this nanocatalyst can be easily recovered and reused for at least six cycles without deterioration in catalytic activity. Graphical Abstract: [Figure not available: see fulltext.]
- Razavi, Nasrin,Akhlaghinia, Batool,Jahanshahi, Roya
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p. 360 - 373
(2017/02/18)
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- Thiophene Methanimine–Palladium Schiff Base Complex Anchored on Magnetic Nanoparticles: A Novel, Highly Efficient and Recoverable Nanocatalyst for Cross-Coupling Reactions in Mild and Aqueous Media: Γ-Fe2O3/AEPH2-TC-Pd Catalyzed Suzuki–Miyaura and Heck–Mizoroki Reactions
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Abstract: In this study, a novel thiophene methanimine–palladium Schiff base complex anchored on decorated γ-Fe2O3 with 2-aminoethyl dihydrogen phosphate (γ-Fe2O3/AEPH2-TC-Pd) was synthesized as a new magnetically separable nanocatalyst. Characterization of the new designed nanocatalyst was performed successfully using different techniques such as FT-IR, XRD, XPS, TEM, TGA, VSM, ICP and elemental analysis. This nanocatalyst presented a superb catalytic activity for Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions. The most important features of the prepared catalytic system which makes the current protocol more beneficial from both industrial and environmental viewpoints are its ease of recovery and reusability up to nine cycles without appreciable loss of the catalytic performance, as well as accomplishing the reactions under mild conditions in aqueous media which is a great challenge in some cross-coupling reactions. Graphical Abstract: [Figure not available: see fulltext.].
- Jahanshahi, Roya,Akhlaghinia, Batool
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p. 2640 - 2655
(2017/09/06)
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- Identification of the Privileged Position in the Imidazo[1,2-a]pyridine Ring of Phosphonocarboxylates for Development of Rab Geranylgeranyl Transferase (RGGT) Inhibitors
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Members of the Rab GTPase family are master regulators of vesicle trafficking. When disregulated, they are associated with a number of pathological states. The inhibition of RGGT, an enzyme responsible for post-translational geranylgeranylation of Rab GTPases represents one way to control the activity of these proteins. Because the number of molecules modulating RGGT is limited, we combined molecular modeling with biological assays to ascertain how modifications of phosphonocarboxylates, the first reported RGGT inhibitors, rationally improve understanding of their structure-activity relationship. We have identified the privileged position in the core scaffold of the imidazo[1,2-a]pyridine ring, which can be modified without compromising compounds' potency. Thus modified compounds are micromolar inhibitors of Rab11A prenylation, simultaneously being inactive against Rap1A/Rap1B modification, with the ability to inhibit proliferation of the HeLa cancer cell line. These findings were rationalized by molecular docking, which recognized interaction of phosphonic and carboxylic groups as decisive in phosphonocarboxylate localization in the RGGT binding site.
- Ka?mierczak, Aleksandra,Kusy, Damian,Niinivehmas, Sanna P.,Gmach, Joanna,Joachimiak, ?ukasz,Pentik?inen, Olli T.,Gendaszewska-Darmach, Edyta,B?azewska, Katarzyna M.
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supporting information
p. 8781 - 8800
(2017/11/15)
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- Intrinsic low dielectric constant polyimides: Relationship between molecular structure and dielectric properties
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Low dielectric organic materials have been studied extensively, however, the relationship and regularity between the molecular structure and the dielectric properties is still not clear and barely reported. In this study, we report the synthesis of three polyimides (PPy6F, mBPPy6F and mTPPy6F) containing the same diphenylpyridine core structure but different side-chains with varied number of benzene rings. The polyimides PPy6F, mBPPy6F and mTPPy6F which contain one, two and three benzene rings in the pendant group, respectively, show intrinsic dielectric constant k values of 2.81 (PPy6F), 2.61 (mBPPy6F) and 2.44 (mTPPy6F). The reason for the reduced k value with increasing number of benzene rings in the pendant group is discussed through the investigation of morphology, density and water absorption properties of these polyimides. This discovery provides us with a new and easy strategy to obtain lower dielectric polymers. Polyimide mTPPy6F shows excellent comprehensive properties, with a high glass transition temperature (Tg) of 342 °C, a 5 wt% loss temperature (Td,5%) of 551 °C, tensile strength of 105 MPa, low moisture absorption of only 0.61% and good solubility in common organic solvents.
- Bei, Runxin,Qian, Chao,Zhang, Yi,Chi, Zhenguo,Liu, Siwei,Chen, Xudong,Xu, Jiarui,Aldred, Matthew P.
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p. 12807 - 12815
(2017/12/26)
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- Mono- and dinuclear cyclopalladates as catalysts for Suzuki–Miyaura cross-coupling reactions in predominantly aqueous media
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Suzuki–Miyaura cross-coupling reactions of aryl halides with arylboronic acids were performed in predominantly aqueous media employing two mono- and two dinuclear cyclopalladated complexes as catalysts. These complexes are [Pd(HL)Cl] (I), [Pd(L)(PPh3)] (II), [Pd2(μ-dppb)(L)2] (III) and [Pd2(μ-dppf)(L)2] (IV); where H2L, dppb and dppf represent 4-methoxy-N′-(mesitylidene)benzohydrazide, 1,4-bis(diphenylphosphino)butane and 1,1′-bis(diphenylphosphino)ferrocene, respectively. The reactions were conducted using potassium carbonate as base in presence of tetrabutylammonium bromide (TBAB) at 70/90 °C in dimethylformamide–water (1:20) mixture. Among the four catalysts used, the dinuclear complex IV turned out to be the most effective and afforded moderate to excellent yields with broad substrate scope.
- Babu, G. Narendra,Pal, Samudranil
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p. 1000 - 1005
(2017/02/18)
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