- Preparation and catalytic evaluation of a palladium catalyst deposited over two-dimensional zeolite ITQ-2 modified with N-donor groups
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Two-dimensional zeolite ITQ-2 was reacted successively with (3-chloropropyl)triethoxysilane, 2-(N,N-diethylamino)ethylamine, and ammonia to give a support bearing the =Si(CH2)3NHCH 2CH2NEt2 groups at the surface. Subsequent treatment with palladium(II) acetate afforded an immobilized palladium catalyst 3, which was tested in the Heck coupling of n-butyl acrylate with bromobenzene to give n-butyl cinnamate (4). This (pre)catalyst, which acts as a source of active metal species for the reaction occurring in the liquid phase, showed good activity in N,N-dimethylformamide and N,N-dimethylacetamide at 150 °C. Reaction tests with different bases revealed a pronounced effect of the base additive on the course of the catalyzed process in terms of both the activity (yield of the coupling product) and selectivity [amount of n-butyl 3,3-diphenylacrylate (5) resulting from twofold arylation]. Among the hydrated bases, the best yields of 4 were obtained in reactions performed in the presence of CH3CO2Na·3H2O and Na 3PO4·12H2O, while that with Na 2CO3·10H2O furnished considerably worse results. The use of the respective anhydrous bases not only decreased the yield of 4 but also incited the formation of the unwanted doubly arylated product 5.
- ?těpni?ka, Petr,K?e?ková, Pavlína,Semler, Miloslav,?ejka, Ji?í
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- A comparative study of some Pd-catalysed Heck reactions in polar- and aqueous biphasic media
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A comparative study of some Pd-catalysed reactions was carried out making use of various ligands and catalyst precursors in polar polar/aqueous biphasic media, the results of which assist in the judicious selection of the appropriate reaction conditions f
- Williams,Lombard,Holzapfel
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- Synthesis and activity evaluation of a FeCl2-promoted palladium hollow nano-sphere heterogeneous catalyst in Mizoroki–Heck coupling reactions
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A high-active, high-quality, and high-yield hollow Pd–PVP–Fe (palladium–poly(N-vinylpyrrolidone)–iron) nano-sphere catalyst with cubic structure was synthesized via a cheap method without using any support. This catalyst exhibited excellent catalytic activity in the Mizoroki–Heck reactions of less reactive chlorobenzene and some aryl bromides with n-butyl acrylate. The catalyst was fully characterized using SEM (scanning electron microscopy), EDX (energy dispersive X-ray spectroscopy), TEM (transmission electron microscopy), HRTEM (high resolution TEM), SAED (selected area electron diffraction) pattern, XRD (X-ray diffraction spectroscopy), FT-IR (Fourier transform infrared spectrophotometry), UV–Vis Spectrophotometry, Zeta sizer, and AAS (atomic absorption spectrometry). Effects of FeCl2·4H2O and PVP concentrations as well as their compatibility with palladium in the catalytic system were investigated. The catalytic property of the catalyst can be controlled by adjusting the proportion of Fe0, Pd0, and PVP concentration. The reused catalyst showed excellent activity as well as negligible leaching of the metal nanostructures into solution from the catalyst system.
- Abadi, Parvaneh Ghaderi-Shekhi,Hajian, Gelareh,Joshaghani, Mohammad,Nadri, Shirin,Rafiee, Ezzat
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- A supported aqueous phase catalyst coating in micro flow Mizoroki-Heck reaction
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The application of a supported aqueous phase catalyst (SAPC) coating was investigated for the Mizoroki-Heck reaction in micro flow and favorably compared to the use of an SAPC in a batch system. In batch, an 83% yield was observed after 4 h at 180 °C with a catalyst loading of 0.4 mol %, while in flow a residence time of 2.9 min provided a 21% yield with only 0.01 mol % catalyst loading. In batch the SAPC could be re-used twice without any significant loss in yield, but further re-use was prevented due to problematic accumulation of an ammonium salt. In the micro flow system, this problem could be overcome by adding water to the product flow prior to cooling, allowing even more effective use of the catalyst.
- Stouten, Stefan C.,Wang, Qi,No?l, Timothy,Hessel, Volker
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- Continuous microflow synthesis of butyl cinnamate by a Mizoroki-Heck reaction using a low-viscosity ionic liquid as the recycling reaction medium
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A continuous microflow system was developed with efficient catalyst recycling for a Mizoroki-Heck reaction of iodobenzene with butyl acrylate, using a low-viscosity ionic liquid ([bmim]-NTf2) as the reaction medium. Using a CPC CYTOS Lab System
- Liu, Shifang,Fukuyama, Takahide,Sato, Masaaki,Ryu, Ilhyong
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- Palladium(0) deposited on PAMAM dendrimers as a catalyst for C-C cross coupling reactions
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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 crosscoupling 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 K2CO3 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.
- Borkowski, Tomasz,Subik, Pawel,Trzeciak, Anna M.,Wolowiec, Stanislaw
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- Comparison of activity and selectivity of various metal-TPPTS complex catalysts in ethylene glycol-toluene biphasic heck vinylation reactions of iodobenzene
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Heck vinylation reactions of iodobenzene were performed with various metal-TPPTS complexes and potassium acetate in a hipbasic mode using ethylene glycol and toluene. The activity, selectivity, stability and recycle performance of these catalytic systems,
- Bhanage,Zhao,Shirai,Arai
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- Structure and Reactivity of "Unusual" N-Heterocyclic Carbene (NHC) Palladium Complexes Synthesized from Imidazolium Salts
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The reaction between palladium acetate and IMES·HCl leads to the formation of a novel palladium complex. The X-ray crystal structure analysis reveals that the palladium is C(2) bound to one NHC ligand (the normal binding mode), whereas the second ligand i
- Lebel, Helene,Janes, Marc K.,Charette, Andre B.,Nolan, Steven P.
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- Pd-PVP colloid as catalyst for Heck and carbonylation reactions: TEM and XPS studies
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Pd-PVP colloid (stabilized with polyvinylpyrrolidone) with a diameter of 19.8 nm in [Bu4N]Br medium catalyzes Heck coupling of bromobenzene with butyl acrylate and methoxycarbonylation of iodobenzene reactions. Oxidative addition of PhI or PhBr to Pd-PVP as the first step of a catalytic reaction was confirmed by TEM and XPS measurements. TEM studies showed significant reduction of Pd nanoparticle size after their reaction with PhX (X = I, Br) and [Bu 4N]X (X = Cl, Br, I). The biggest shift of the center of nanoparticle size distribution, from 19.8 nm to 7.6 nm, was found when Pd-PVP reacted with PhI and [Bu4N]Br. The formation of [Bu4N] 2[Pd(Ph)Br3]- and [Bu4N]2[PdBr 4]-type complexes in that system was evidenced by XPS and UV-vis spectra.
- Gniewek, Andrzej,Trzeciak, Anna M.,Ziolkowski, Jozef J.,Kepinski, Leszek,Wrzyszcz, Jozef,Tylus, Wlodzimierz
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- Palladium supported aminobenzamide modified silica coated superparamagnetic iron oxide as an applicable nanocatalyst for Heck cross-coupling reaction
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An applicable palladium-based nanocatalyst was constructed through the immobilization of palladium onto 2-aminobenzamide functionalized silica coated superparamagnetic iron oxide magnetic nanoparticles. The nanocatalyst (named as Pd@ABA@SPIONs@SiO2) was characterized by several characterization methods, including scanning electron microscope (SEM), transmission electron microscopy (TEM), vibrating-sample magnetometry (VSM), energy-dispersive X-ray spectroscopy (EDS), dynamic light scattering (DLS), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma (ICP), and X-ray photoelectron spectroscopy (XPS) analyses. Microscopy results showed that the nanoparticles are spherical in shape with 20–25 nm size. The size of the nanoparticles was confirmed by the DLS method. The superparamagnetic nature of the catalyst was confirmed by the VSM method. The successful functionalization of SPIONs@SiO2 was confirmed by FT-IR spectroscopy. The presence of palladium in the structure of the nanocatalyst was illustrated by XRD and EDS analysis. Also using XPS technique, the oxidation state of palladium in Pd@ABA@SPIONs@SiO2 was determined zero before and after the catalyst was applied in Mizoroki-Heck reaction. Several aryl halides and alkenes were reacted in the presence of the nanocatalyst and formed the corresponding products in high isolated yields. The nanocatalyst showed very good reusability and did not decrease its activity after 10 sequential runs. Density functional theory (DFT) calculation was performed to provide a mechanism for the reaction and confirmed the role of the palladium catalyst in the reaction function.
- Fatahi, Yousef,Ghaempanah, Aram,Ma?mani, Leila,Mahdavi, Mohammad,Bahadorikhalili, Saeed
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- Green and sustainable palladium nanomagnetic catalyst stabilized by glucosamine-functionalized Fe3O4@SiO2 nanoparticles for Suzuki and Heck reactions
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A novel magnetic and heterogeneous palladium-based catalyst stabilized by glucosamine-functionalized magnetic Fe3O4@SiO2 nanoparticle was synthesized. The strategy relies on the covalently bonding of glucosamine to cyanuric chloride-functionalized magnetic nanoparticles followed by complexation with palladium. The structure of magnetic nanocatalyst was fully determined by FT-IR, XRD, DLS, FE-SEM, TEM, ICP, UV-Vis, TGA, VSM, and EDX. The obtained results confirmed that the palladium nanoparticles stabilized by glucosamine immobilized onto the magnetic support exhibited high activity in cross-coupling reactions of Suzuki-Miyaura and Mizoroki-Heck. Various aryl halides were coupled with arylboronic acid (Suzuki cross-coupling reaction) and olefins (Heck reactions) under the green conditions to provide corresponding products in high to excellent yields. Interestingly, the catalyst can be easily isolated from the reaction media by magnetic decantation and can subsequently be applied for consecutive reaction cycles (at least seven times) with no notable reduction in the catalytic activity.
- Eslahi, Hassan,Sardarian, Ali Reza,Esmaeilpour, Mohsen
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- NiFe2O4@SiO2@ZrO2/SO42-/Cu/Co nanoparticles: A novel, efficient, magnetically recyclable and bimetallic catalyst for Pd-free Suzuki, Heck and C-N cross-coupling reactions in aqueous media
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The novel heterogeneous bimetallic nanoparticles of Cu-Co were synthesized based on magnetic nanoparticles, and the magnetic nanocatalyst was characterized by XRD, FE-SEM, EDX mapping, BET, TEM, HRTEM, FTIR, TGA, and VSM. This catalyst was successfully applied as a recyclable magnetically catalyst in Heck, Suzuki, and C-N cross-coupling reactions with various aryl halides (iodides, bromides, and chlorides as challengeable substrates), with olefins, phenylboronic acid, and amines, respectively. We considered the rise of synergetic effects from the different Lewis acid and Br?nsted acid sites present in the catalyst. The catalyst was synthesized with cheap, available materials and a simple synthesis method. The catalyst can be separated easily using an external magnet. It was recycled for more than ten runs without a sensible loss of its catalytic activity, and no significant leaching of the Cu and Co quantity was observed. The significant benefits of the method are high-level generality, simple operation, and there are no heavy metals and toxic solvents. This is a quick, easy, efficacious and environmentally friendly protocol, and no by-products are formed in the reaction. These features make it an appropriate practical alternative protocol. In comparison with recent works, the other advantage of this catalyst is the synthesis of a wide variety of C-C and C-N bond derivatives (more than 40 derivatives). The other significant advantage is the low temperature of the reaction and the use of the least possible amount of the catalyst (0.003 g). The efficiency was good to excellent and the catalyst selectivity has been high. We aspire that our study inspires more interest to design novel catalysts based on using low-cost metal ions (such as cobalt and copper) in the cross-coupling reactions. This journal is
- Alavi G., Seyyedeh Ameneh,Nasseri, Mohammad Ali,Kazemnejadi, Milad,Allahresani, Ali,Hussainzadeh, Mahdi
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p. 7741 - 7757
(2021/05/13)
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- Introduction of a Recyclable Basic Ionic Solvent with Bis-(NHC) Ligand Property and The Possibility of Immobilization on Magnetite for Ligand- and Base-Free Pd-Catalyzed Heck, Suzuki and Sonogashira Cross-Coupling Reactions in Water
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A new versatile and recyclable NHC ligand precursor has been developed with ligand, base, and solvent functionalities for the efficient Pd-catalyzed Heck, Suzuki and Sonogashira cross-coupling reactions under mild conditions. Furthermore, NHC ligand precursor was immobilized on magnetite and its catalytic activity was also evaluated towards the coupling reactions as a heterogeneous catalyst. The NHC ligand precursor was prepared with imidazolium functionalization of TCT followed by a simple ion exchange by hydroxide ions. However, the results revealed an excellent catalytic activity for the both homogeneous and heterogeneous catalytic systems. 1.52?g.cm?3 and 1194 cP was obtained for the density and viscosity of the NHC ligand precursor respectively. On the other hand, the heterogeneous type could be readily recovered from the reaction mixture and reused for several times while preserving its properties. Heterogeneous nature of the magnetic catalyst was studied by hot filtration, mercury poisoning, and three-phase tests. High to excellent yields were obtained for all entries for the both homogeneous and heterogeneous catalysts, which reflects the high consistency of the catalyst. Graphic Abstract: [Figure not available: see fulltext.]
- Min, Qingwang,Miao, Penghua,Chu, Deyu,Liu, Jinghan,Qi, Meijuan,Kazemnejadi, Milad
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p. 3030 - 3047
(2021/02/16)
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- Palladium and silk fibroin-containing magnetic nano-biocomposite: a highly efficient heterogeneous nanocatalyst in Heck coupling reactions
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Supported metal catalysts, for instance, palladium, are one of the foundations of chemical reactions, especially in C–C bond formation. The present study reports preparation of a magnetically separable palladium-supported nano-biocomposite with a low cost and easy immobilization technique. Fibroin, a natural biodegradable polymer, was used through an in situ method to cover the Fe3O4 nanoparticles to make a nano-biocomposite followed by anchoring palladium on the fibroin surface. The morphology and the structure of palladium-supported nano-biocomposite Fe3O4@fibroin-Pd were characterized by FT-IR, XRD, TGA, SEM, EDX, and TEM techniques. Consequently, the nanocatalyst activity was evaluated in the Heck coupling reactions. Only a very small amount of the nanocatalyst was employed in the reaction, and it showed excellent catalytic activity; in most cases more than 90% efficiency. The significant advantages of employing this nanocatalyst include high catalytic activity, short reaction times, easy separation of the nanocatalyst with an external magnet and great reusability. The results demonstrated that the used nanocatalysts were very active for four consecutive reaction rounds.
- Nouri Parouch, Ahmad,Koukabi, Nadiya,Abdous, Elham,Shobeiri, Seyed Amin
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p. 3165 - 3177
(2021/05/21)
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- Hypervalent iodine(iii) induced oxidative olefination of benzylamines using Wittig reagents
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We have developed hypervalent iodine(iii) induced oxidative olefination of primary and secondary benzylamines using 2C-Wittig reagents, which provides easy access to α,β-unsaturated esters. Mild reaction conditions, good to excellent yields with high (E) selectivity, and a broad substrate scope are the key features of this reaction. We have successfully carried out the gram-scale synthesis of α,β-unsaturated esters.
- Ramavath, Vijayalakshmi,Rupanawar, Bapurao D.,More, Satish G.,Bansode, Ajay H.,Suryavanshi, Gurunath
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p. 8806 - 8813
(2021/05/26)
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- Pd supported on clicked cellulose-modified magnetite-graphene oxide nanocomposite for C-C coupling reactions in deep eutectic solvent
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Cellulose-modified magnetite-graphene oxide nanocomposite was prepared via click reaction and utilized for immobilization of palladium (Pd) nanoparticles without using additional reducing agent. The abundant OH groups of cellulose provided the uniform dispersion and high stability of Pd nanoparticles, while magnetite-graphene oxide as a supporting material offered high specific surface area and easy magnetic separation. The as-prepared nanocomposite served as a heterogeneous catalyst for the Heck and Sonogashira coupling reactions in various hydrophilic and hydrophobic deep eutectic solvents (DESs) as sustainable and environmentally benign reaction media. Among the fifteen DESs evaluated for coupling reactions, the hydrophilic DES composed of dimethyl ammonium chloride and glycerol exhibited the best results. Due to the low miscibility of catalyst and DES in organic solvents, the separated aqueous phase containing both of the catalyst and DES can be readily recovered by evaporating water and retrieved eight times with negligible loss of catalytic performance.
- Karimi, Sabah,Masteri-Farahani, Majid,Niakan, Mahsa,Shekaari, Hemayat
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- Fe-MIL-101 modified by isatin-Schiff-base-Co: a heterogeneous catalyst for C-C, C-O, C-N, and C-P cross coupling reactions
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A metal-organic framework functionalized with a cobalt-complex is preparedviapost-synthetic modification of Fe-MIL-101-NH2. Initially, Fe-MIL-101-NH2reacted with isatin to produce Fe-MIL-101-isatin-Schiff-base, which can anchor the cobalt by the addition of cobalt acetate. The resulting MOF-Co catalyst is characterized by employing multiple techniques. This new modified MOF acts as a heterogeneous and recyclable catalyst for efficient Ullmann, Buchwald-Hartwig, Hirao, Hiyama and Mizoroki-Heck cross-coupling reactions of several aryl halides/phenylboronic acid/phenyltosylate with phenols, anilines/heterocyclic amines, triethyl phosphite, triethoxyphenylsilane and alkenes and generates the expected coupling products in good to high yields.
- Farrokhi, Alireza,Rouzifar, Majid,Sansano, José Miguel,Sobhani, Sara
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p. 19963 - 19976
(2021/11/12)
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- A comparative study of palladium-based coordination compounds with bidentate (N,N, P,P and P,O) ligands; Design, synthesis, X-ray structural, catalytic activity and DFT studies
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This account describes our recent studies on four new asymmetric cyclometallated Pd(II) complexes with a formula [L1 → Pd ← L2](ClO4) (L1 = benzylamine and L2 = bis (diphenylphosphino) methane oxide (
- Babaee, Heshmatollah,Javad Sabounchei, Seyyed,Naghipour, Ali,Notash, Behrouz,Sayadi, Mohsen,Sedghi, Asieh
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- Palladium nanoparticles encapsulated in polyimide nanofibers: An efficient and recyclable catalyst for coupling reaction
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In this study, palladium-encapsulated poly(amic acid) (Pd@PAA) nanofibers were prepared by electrospinning, followed by thermal imidization to synthesize palladium-encapsulated polyimide (Pd@PI) nanofibers. Scanning electron microscopy (SEM) images confirmed the preparation of uniform and smooth Pd@PAA and Pd@PI nanofibers. Thermogravimetric analysis (TGA) results reveal that the Pd@PI nanofibers possessed excellent thermal stability. The dispersion of palladium nanoparticles in the polyimide nanofibers was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The catalysis results show that this Pd@PI fibrous catalyst was very efficient to catalyze the cross-coupling reactions of aromatic iodides with n-butyl acrylate (Heck reaction) or phenylboronic acid derivatives (Suzuki reaction) to afford the desired products in good to excellent yields. Moreover, the Pd@PI catalyst could be easily separated and recovered from the reaction mixture by simple filtration due to the regular fibrous structure and reused for 10 times for both Heck and Suzuki reactions without obvious loss of its initial catalytic activity. Thus, the Pd@PI nanofiber catalyst holds great potential in chemical industry in terms of its excellent catalytic activity and stability.
- Du, Yijun,Gou, Faliang,Gao, Danning,Liu, Zhifeng,Shao, Linjun,Qi, Chenze
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- Phenanthroline functionalized polyacrylonitrile fiber with Pd(0) nanoparticles as a highly active catalyst for the Heck reaction
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A series of polyacrylonitrile fibers (PANF) functionalized with nitrogen-containing ligands were prepared and then used to synthesize fiber-supported Pd(0) nanoparticle catalysts. The phenanthroline-functionalized PANF with immobilized Pd(0) nanoparticles (PANPhenF-Pd(0)) had the best catalytic activity for the Heck reaction under solvent-free conditions. The PANPhenF-Pd(0) efficiently stabilized the nanoparticles and they were well-dispersed with Pd(0) particle sizes of about 3 nm. The PANPhenF-Pd(0) structure was further characterized by a variety of instrumental methods. A probable mechanism based on the fiber's microenvironment is proposed for the Heck reaction catalyzed by PANPhenF-Pd(0). The PANPhenF-Pd(0) catalyst is easily recovered from the reaction system and can be used up to six times with only a slight decrease in catalytic activity and with low Pd leaching. The PANPhenF-Pd(0) catalyst also has excellent catalytic activity for gram-scale use.
- Xiao, Jian,Zhang, Haonan,Ejike, Anyaegbu Chima,Wang, Lu,Tao, Minli,Zhang, Wenqin
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- Photoinduced Oxidative Alkoxycarbonylation of Alkenes with Alkyl Formates
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A photoinduced oxidative alkoxycarbonylation of alkenes initiated by intermolecular addition of alkoxycarbonyl radicals has been demonstrated. Employing alkyl formates as alkoxycarbonyl radical sources, a range of α,β-unsaturated esters were obtained with good regioselectivity and E selectivity under ambient conditions.
- Tang, Wan-Ying,Chen, Ling,Zheng, Ming,Zhan, Le-Wu,Hou, Jing,Li, Bin-Dong
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supporting information
p. 3939 - 3943
(2021/05/26)
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- Olefin Metathesis, p-Cresol, and the Second Generation Grubbs Catalyst: Fitting the Pieces
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p-Cresol as additive to the Grubbs second generation catalyst (GII) allows the cross-metathesis of acrylates with prop-1-en-1-ylbenzenes under conditions that only give the prop-1-en-1-ylbenzene self-metathesis product in the absence of cresol. NMR and IR spectroscopy, MALDI-TOF MS and XPS supported the formation of a ruthenium benzylidene with hydrogen bonds between p-cresol and the chloride ligands of GII. XPS furthermore confirmed p-cresol to increase the binding energies of the GII Ru 3d5/2, 3d3/2, 3p3/2 and 3p1/2 photoelectron lines, whereas 1H NMR spectroscopy indicated the carbene carbon and hydrogen to be shielded. It is thus postulated that p-cresol allows for more facile interaction between electron-deficient compounds and the ruthenium benzylidene by decreasing the electron density on the metal center and increasing the electron density on the carbene.
- Swart, Marthinus R.,Twigge, Linette,Erasmus, Elizabeth,Marais, Charlene,Bezuidenhoudt, Barend C. B.
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supporting information
p. 1752 - 1762
(2021/05/06)
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- Ruthenium-Catalyzed Oxidative Cross-Coupling Reaction of Activated Olefins with Vinyl Boronates for the Synthesis of (E, E)-1,3-Dienes
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An oxidative cross-coupling reaction between activated olefins and vinyl boronate derivatives has been developed for the highly stereoselective construction of synthetically useful (E,E)-1,3-dienes. The highlight of this reaction is that exclusive stereoselectivity (only E,E-isomer) was achieved from a base-free, ligand-free, and mild catalytic condition with a less expensive [RuCl2(p-cymene)]2 catalyst.
- Dethe, Dattatraya H.,Beeralingappa, Nagabhushana C.,Uike, Amar
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p. 3444 - 3455
(2021/02/16)
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- Benzyne-Mediated Esterification Reaction
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A benzyne-mediated esterification of carboxylic acids and alcohols under mild conditions has been realized, which is made possible via a selective nucleophilic addition of carboxylic acid to benzyne in the presence of alcohol. After a subsequent transesterification with alcohol, the corresponding esters can be produced efficiently. This benzyne-mediated protocol can be used on the modification of Ibuprofen, cholesterol, estradiol, and synthesis of nandrolone phenylpropionate. In addition, benzyne can also be used to promote lactonization and amidation reaction.
- Li, Yang,Shi, Jiarong,Zhao, Jinlong
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supporting information
p. 7274 - 7278
(2021/10/01)
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- Ligand-Free Catalytic Cross-Coupling in the System Aryl Halide–Arylacetylene–Alkene
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Abstract: Three-component cross-coupling in the system aryl halide–arylacetylene–alkenein the presence of simplest ligand-free palladium catalysts gave products ofboth 1+1+1-coupling and cross-dimerization of arylacetylene with alkene. Thepossibility of c
- Lagoda,Vidyaeva,Larina,Kurokhtina,Schmidt
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- Preparation method of cinnamate compound
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The invention discloses a preparation method of a cinnamate compound, which comprises the following steps: sequentially adding a diaryl trifluoromethane sulfonic acid iodine compound, an acrylate compound, a palladium complex, an additive and a solvent into a reaction flask, reacting, and stirring at 70-90 DEG C for 15-20 hours; quenching and extracting; drying the extract, filtering, concentrating, and carrying out column chromatography purification to obtain the cinnamate compound. The problems that a traditional reaction catalyst is large in dosage and too high in reaction temperature are effectively solved, the performance of the palladium catalyst can be brought into full play, the palladium catalyst can rapidly conduct coordination reaction on electron-deficient olefin, the use efficiency of the catalyst is improved, the reaction temperature is reduced, a special reaction environment is not needed, raw materials are simple and easy to obtain, and reaction conditions are loose. The preparation method is a low-cost preparation method of the cinnamate compound.
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Paragraph 0026-0027
(2021/01/15)
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- Palladium Ion Catalysed Oxidative C–C Bond Formation Reactions in Arylboronic Acid: Application of Cordierite Monolith Coated Catalyst
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Abstract: Catalytic efficiency of palladium ion substituted in TiO2, Ti0.97Pd0.03O1.97 is successfully exploited for the oxidative homocoupling of arylboronic acid and oxidative Heck coupling reactions between arylboronic acid and olefins. The reaction protocol provides direct approach to synthesize biphenyls and cinnamates from moderate to good yield with good functional group tolerance. As a result, 11 symmetrical biaryls and 14 cinnamates were synthesized from readily available arylboronic acids. Ti0.97Pd0.03O1.97 powder catalyst is synthesized by solution combustion method and characterized by powder X-ray diffraction. The C–C bond formation reactions were carried out by catalyst cartridge method using Ti0.97Pd0.03O1.97 catalyst coated cordierite monolith. Coating of the catalyst on a cordierite monolith enhanced the applicability of the catalyst and made handling and recycling of the catalyst very easy. Catalyst was recovered and recycled for eight times in both homocoupling and oxidative Heck coupling reactions. The turnover number for both the reactions found to be 443 and 424, respectively. Graphic Abstract: [Figure not available: see fulltext.].
- Bhat, Shrikanth K.,Prasanna,Dasappa, Jagadeesh Prasad,Hegde
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p. 2911 - 2927
(2020/03/31)
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- Chemical-Reductant-Free Electrochemical Deuteration Reaction using Deuterium Oxide
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We report a method for the electrochemical deuteration of α,β-unsaturated carbonyl compounds under catalyst- and external-reductant-free conditions, with deuteration rates as high as 99 percent and yields up to 91 percent in 2 h. The use of graphite felt for both the cathode and the anode was key to ensuring chemoselectivity and high deuterium incorporation under neutral conditions without the need for an external reductant. This method has a number of advantages over previously reported deuteration reactions that use stoichiometric metallic reductants. Mechanistic experiments showed that O2 evolution at the anode not only eliminates the need for an external reductant but also regulates the pH of the reaction mixture, keeping it approximately neutral.
- Cheng, Xu,Li, Guigen,Liu, Ruoyu,Liu, Xu,Qiu, Jiaxing
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supporting information
p. 13962 - 13967
(2020/06/10)
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- L-Methionine-Pd complex supported on hercynite as a highly efficient and reusable nanocatalyst for C-C cross-coupling reactions
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A "green" method was suggested for the synthesis of hercynite magnetic nanoparticles (MNPs) as a novel heterogeneous catalytic support to immobilize homogeneous complexes. l-Methionine-Pd was immobilized on the surface of hercynite MNPs by a simple, rapid, and convenient route. The structure and composition of the prepared Hercynite@l-Methionine-Pd MNPs were characterized by X-ray diffraction spectroscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma-optical emission spectrometry, scanning electron microscopy, X-ray mapping, thermogravimetric analysis and vibrating-sample magnetometry (VSM). Besides, they were applied as green nanocatalysts for Suzuki and Heck cross-coupling reactions. Hercynite@l-Methionine-Pd MNPs offer several advantages (simple synthetic method under green conditions, thermal and chemical stability during organic reactions, short reaction times, high yields of products, excellent selectivity and easy work-up procedure). Moreover, the recycled nanocatalyst was reused for at least five cycles with no significant loss of activity. The hot filtration test indicated heterogeneous catalysis for Suzuki and Heck cross-coupling reactions. This work is useful for the development and application of a magnetically recoverable Pd nanocatalyst on the basis of green-chemistry principles.
- Mohammadi, Masoud,Ghorbani-Choghamarani, Arash
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supporting information
p. 2919 - 2929
(2020/03/03)
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- Shuttling Catalyst: Facilitating C?C Bond Formation via Cross-Couplings with a Thermoresponsive Polymeric Ligand
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A poly(ethylene glycol) (PEG) linked ortho-MeO-phenyldicyclohexylphosphine (MeO-WePhos) ligand has been synthesized to promote Pd-catalyzed carbon-carbon bond formation by cross-couplings including Sonogashira, Heck, Hiyama and Stille reactions, providing corresponding (hetero)aryl substituted alkynes, alkenes and bi(hetero)aryls in good to excellent isolated yields with low Pd loadings. Facilitated by the lower critical solution temperature behaviour of the polymeric monophosphine ligand, the metal-complex could rapidly shuttle between organic and water phases as regulated by temperature, enabling highly efficient catalyst recycling via a simple phase separation. The chemical structure of ligand was determined by matrix-assisted laser desorption/ionization-time of flight mass spectrometry, nuclear magnetic resonance spectrometry and size-exclusion chromatography measurements. Notably, as demonstrated by the inductively coupled plasma-atomic emission spectrometry measurement, 98% Pd was kept in the water phase after 6 cycles of catalyst recycling experiments. Given the profound impact of transition-metal-catalyzed covalent bond formation and the increasing demand of sustainable chemistry, this work provides an alternative method to conduct cross-couplings with a polymeric shuttling catalyst.
- Wang, Erfei,Zhang, Jiawei,Zhong, Zhuoran,Chen, Kaixuan,Chen, Mao
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p. 419 - 423
(2020/01/08)
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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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p. 1059 - 1072
(2020/01/06)
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- C–C Cross-Coupling Reactions of Organosilanes with Terminal Alkenes and Allylic Acetates Using PdII Catalyst Supported on Starch Coated Magnetic Nanoparticles
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Starch coated magnetic nanoparticles supported palladium catalyst has been explored to perform C–C cross coupling reactions, such as oxidative Heck coupling and Tsuji–Trost allylic coupling using organosilicon compounds as one of the coupling partners. The biopolymer coated magnetic catalyst was very easy to recover magnetically and was efficiently recycled in the subsequent batches. All the reactions were performed in air and thus the necessity of air and moisture free reaction condition is avoided. The present protocols show wide substrate scope and good yields of the products.
- Patra, Debabrata,Panja, Subir,Saha, Amit
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supporting information
p. 878 - 883
(2020/02/13)
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- A hydrophilic heterogeneous cobalt catalyst for fluoride-free Hiyama, Suzuki, Heck and Hirao cross-coupling reactions in water
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A hydrophilic heterogeneous cobalt catalyst of chitosan, denoted as mTEG-CS-Co-Schiff-base, has been successfully prepared. This newly synthesized catalyst was characterized by different methods such as XRD, FE-SEM, TEM, TGA, FT-IR, 13C{1H} CP/MAS NMR, XPS and ICP analyses. The catalyst displayed excellent activity for the palladium and fluoride-free Hiyama, Suzuki, Heck and Hirao reactions of various aryl iodides, bromides and chlorides (i.e., the most challenging aryl halides which are cheaper and more widely available than aryl iodides and bromides) in water. The presence of triethylene glycol tags with hydrophilic character on the Co-complex supported on chitosan provides dispersion of the catalyst particles in water, which leads to higher catalytic performance and also facile catalyst recovery by successive extraction. It was reused for at least six successive runs without any discernible decrease in its catalytic activity or any remarkable changes in catalyst structure. The use of water as a green solvent, without requiring any additive or organic solvent, as well as use of a low cost and abundant cobalt catalyst instead of expensive Pd catalysts along with the catalyst recovery and scalability, make this method favorable from environmental and economic points of view for the C-C and C(sp2)-P coupling reactions. Notably, this is the first report on the application of a cobalt catalyst in Hiyama reactions.
- Sobhani, Sara,Hosseini Moghadam, Hadis,Skibsted, J?rgen,Sansano, José Miguel
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p. 1353 - 1365
(2020/03/11)
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- Fe3O4-Lignin@Pd-NPs: A highly efficient, magnetically recoverable and recyclable catalyst for Mizoroki-Heck reaction under solvent-free conditions
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Palladium nanoparticles (Pd-NPs) were synthesized under green conditions in water by chemical reduction of PdCl2 with NaOH and supported by Fe3O4-Lignin. Fe3O4-Lignin is an organic–inorganic hybrid core-shell was synthesized by sonication of a mixture of Fe3O4-NPs (20 nm) and alkali lignin. The new materials Fe3O4-Lignin and Fe3O4-Lignin@Pd-NPs were characterized by PXRD, SEM and FT-IR spectroscopy. The Fe3O4-Lignin@Pd-NPs was further confirmed by UV–Visible spectroscopy, TEM, EDX, HRICP-AES and TGA/DTA. The average size of Pd-NPs determined from PXRD was 5–10 nm. The amount of palladium loaded on Fe3O4-Lignin obtained from EDX analysis was 26.63percent by mass. The amount of Fe and Pd present in the catalyst obtained from HRICP-AES was 11.88 (wt. percent) and 10.90 (wt. percent) respectively per gram of lignin. The catalytic potential of Fe3O4-Lignin@Pd-NPs was evaluated in Mizoroki-Heck C-C coupling reaction. During the optimization studies of reaction between iodobenzene and n-butyl acrylate in various solvents and under solvent-free but aerobic conditions using various inorganic and organic bases, the product n-butyl 3-phenylprop-2-enoate (1a) obtained was as high as 95percent in highly polar solvents as short as in 10 min and 99percent under solvent-free conditions in 3 min at 140 °C using n-Pr3N as base. The scope of the above catalyst was investigated in the Mizoroki-Heck reaction of various aryl/heterocyclic halides and n-butyl acrylate/styrene under optimized solvent-less conditions. The corresponding products were obtained in high yields (73–99percent). The catalyst recovered by magnetic decantation was reused for five times in the C-C coupling reaction between iodobenzene and n-butyl acrylate which yielded 90–95percent of the desired product, 1a.
- Madrahalli Bharamanagowda, Marulasiddeshwara,Panchangam, Raghavendra Kumar
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- Palladium schiff base complex immobilized on magnetic nanoparticles: An efficient and recyclable catalyst for Mizoroki and Matsuda-Heck coupling
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The present work elucidates the catalytic efficiency of palladium Schiff base complex immobilized on amine functionalized magnetic nanoparticles for Heck coupling of structurally different aryl halide/arenediazonium tetrafluoroborate with styrene/acrylate/acrylonitrile. Matsuda-Heck coupling proceeds in aqueous media at room temperature whereas Mizoroki-Heck coupling was carried out at 80 °C. Both reactions were successfully furnished with low catalyst loading. The catalyst was easily separated from reaction mixture and reused up to six times without significant loss of catalytic activity.
- Vibhute, Sandip P.,Mhaldar, Pradeep M.,Shejwal, Rajendra V.,Rashinkar, Gajanan S.,Pore, Dattaprasad M.
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supporting information
(2020/03/23)
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- Catalytic and antibacterial properties of 3-dentate carboxamide Pd/Pt complexes obtained via a benign route
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The complexes PdII(qcq)(OAc) and PtII(qcq)Cl have been synthesized using environmentally benign synthesized ligands and characterized by elemental analyses: Fourier transform infrared spectroscopy, UV–visible spectroscopy, 1H NMR spectroscopy, and X-ray diffraction. The catalytic activity of the complex was assessed, in different media, for the Mizoroki–Heck coupling reaction for typical aryl halides and terminal olefins under aerobic conditions. Since the base and the solvent were found to influence the efficiency of the reaction, reaction conditions, temperature, time, and the amount of K3PO4 and a mixture of H2O/PEG, were optimized. We found, for the Mizoroki–Heck reaction coupling less reactive aryl chloride derivatives with olefins, promising activity for palladium catalysts. The electrochemical behavior of Hqcq and the Pd(II) complex was investigated by cyclic voltammetry and irreversible PdII/I reductions were observed. Hqcq and the Pd(II) and Pt(II) complexes were also screened for their in vitro antibacterial activity. They showed promising antibacterial activity comparable to that of the antibiotic penicillin.
- Kiani, Mahsa,Bagherzadeh, Mojtaba,Meghdadi, Soraya,Fadaei-Tirani, Farzaneh,Schenk-Jo?, Kurt,Rabiee, Navid
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- Encapsulating palladium nanoparticles inside ethylenediamine functionalized and crosslinked chlorinated poly(vinyl chloride) nanofibers as an efficient and stable heterogeneous catalyst for coupling reactions
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Palladium chloride and chlorinated poly (vinyl chloride) (CPVC) mixture were prepared into homogeneous solution, followed by electrospinning to make uniform nanofibers with average diameter of ~460 nm. Then, these composite nanofibers were treated in ethy
- Du, Yijun,Qi, Chenze,Qin, Min,Shao, Linjun,Tao, Hongyu,Wang, Qingqing
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- Preparation method of cinnamate in eutectic solvent (by machine translation)
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The invention discloses a method for preparing cinnamate from a eutectic solvent. A mol of choline chloride, B mol of methanesulfonic acid (p-toluenesulfonic acid) was added to a dry three-port flask, stirred at room temperature for eutectic solvent, C mol of cinnamic acid, D mol of alcohol, 50 °C for reaction, TLC was monitored until reaction was complete. After the completion of the reaction, the reaction liquid is poured into water, extracted with dichloromethane, the organic phase is distilled off to obtain a cinnamate, and the aqueous phase is recovered to obtain a eutectic solvent. The method does not need an organic solvent, and is simple to operate, high in yield, high in product purity, short in reaction time, simple in post-treatment, environmentally friendly and low in cost. (by machine translation)
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Paragraph 0040-0042
(2020/07/02)
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- Coumaric acid derivatives as tyrosinase inhibitors: Efficacy studies through in silico, in vitro and ex vivo approaches
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p-Coumaric acid is a known inhibitor of tyrosinase, an enzyme involved in the initial steps of the melanin synthesis in human and other species. However, its low lipophilicity impairs its penetration through skin and efficacy as antimelanogenic agent indeed. Accordingly, this paper reports the assessment of several coumaric acid derivatives as tyrosinase inhibitors and antimelanogenic agents in in vitro, in silico and ex vivo assays. The compounds were designed with modifications in the aromatic and acid moieties of p-coumaric acid, being the coumarate esters the most promising derivatives. The compounds showed higher tyrosinase inhibitory activity (pIC50 3.7–4.2) than the parent acid, being compounds 1d, 1e and 1f the most potent inhibitors. Docking analysis showed that these esters are competitive inhibitors per se, and act independently of a redox mechanism as suggested by DPPH assays. Moreover, the esters showed efficacy in reducing the melanin deposition in human skin fragments at 0.1% concentration, especially compound 1e. In summary, there is an important equilibria between tyrosinase affinity and lipophilicity that must be considered to get effective antimelanogenic agents with adequate permeability in the skin.
- Fernandes, Jo?o Paulo S.,Ferrarini, Márcio,Mercaldi, Vitória Gallo,Nazato, Lucas Idacir Sbrugnera,Padovani, Giovana,Sufi, Bianca da Silva,Varela, Marina Themoteo
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- Esterification of Tertiary Amides: Remarkable Additive Effects of Potassium Alkoxides for Generating Hetero Manganese–Potassium Dinuclear Active Species
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A catalyst system of mononuclear manganese precursor 3 combined with potassium alkoxide served as a superior catalyst compared with our previously reported manganese homodinuclear catalyst 2 a for esterification of not only tertiary aryl amides, but also tertiary aliphatic amides. On the basis of stoichiometric reactions of 3 and potassium alkoxide salt, kinetic studies, and density functional theory (DFT) calculations, we clarified a plausible reaction mechanism in which in situ generated manganese–potassium heterodinuclear species cooperatively activates the carbonyl moiety of the amide and the OH moiety of the alcohols. We also revealed details of the reaction mechanism of our previous manganese homodinuclear system 2 a, and we found that the activation free energy (ΔG≠) for the manganese–potassium heterodinuclear complex catalyzed esterification of amides is lower than that for the manganese homodinuclear system, which was consistent with the experimental results. We further applied our catalyst system to deprotect the acetyl moiety of primary and secondary amines.
- Akiyama, Shoko,Himo, Fahmi,Hirai, Takahiro,Katayama, Shoichiro,Kato, Daiki,Mai, Binh Khanh,Mashima, Kazushi,Nagae, Haruki
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- Controlling reactivity in the Fujiwara–Moritani reaction: Examining solvent effects and the addition of 1,3-dicarbonyl ligands on the oxidative coupling of electron rich arenes and acrylates
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A palladium-catalysed direct alkenation of electron rich arenes in the presence of K2S2O8 with an acetic acid/1,4-dioxane solvent combination has been developed. The 1,4-dioxane co-solvent dramatically influences the rate of reaction, giving selectively disubstituted alkenes, while the addition of acetylacetone ligands was shown to increase site selectivity for the alkenation of monofunctionalized arenes. The participation of these carbonyl ligands has been confirmed by ESI-MS studies, with some key in situ intermediates in the catalytic cycle identified. A variety of electron rich arenes and olefinic substrates can be utilised in the direct oxidative coupling to give disubstituted alkenes in moderate to good yields.
- Jones, Roderick C.
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supporting information
(2019/12/25)
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- A new approach to large scale production of dimethyl sulfone: A promising and strong recyclable solvent for ligand-free Cu-catalyzed C-C cross-coupling reactions
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Dimethyl sulfone (DMSN) was easily prepared through efficient oxidation of dimethyl sulfoxide (DMSO) and used as a strong and green solvent for organic reactions. A mixture of HNO3/NaOCl was used as an oxidizing agent for efficient oxidation of DMSO to DMSN. The effect of DMSN was evaluated for copper-catalyzed coupling reactions. It is worth noting that DMSN could play the role of a ligand for copper ions. A general survey was accomplished for various types of C-C cross-coupling reactions catalyzed by CuI in DMSN in the absence of any ligand. Moderate to good yields were achieved for Sonogashira, Heck, and Suzuki cross-coupling reactions. Finally, DMSN was recovered and reused for several consecutive runs without any loss of its activity.
- Cheng, Shen,Wei, Wei,Zhang, Xingyu,Yu, Hewei,Huang, Mingming,Kazemnejadi, Milad
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p. 2069 - 2076
(2020/04/07)
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- A highly efficient palladium complex supported on MCM-41 nanocatalyst for Mizoroki–Heck and Suzuki–Miyaura cross-coupling reaction
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Palladium-3,4-dihydroxybenzaldehyde complex supported on MCM-41 was synthesized by a post-grafting method as selective complex a and shows remarkable properties such as thermal and chemical stability, reusable, easily prepared from very cheap materials and can be used as an efficient and versatile catalyst for Mizoroki–Heck and Suzuki–Miyaura cross-coupling reaction. This catalyst was characterized by SEM, TEM, EDX, XRD, FT-IR, TGA, BET and ICP techniques. The synthesized Pd-BS-MCM-41 heterogeneous catalyst could be recovered easily and reused several times without significant loss of its catalytic activity. Further investigations showed that among different aryl halides that used for the synthesis of biaryls and butyl cinnamate derivatives, the reactivity of aryl iodides is higher than aryl bromides, and aryl chlorides. The heterogeneity manner of this nanocatalyst was confirmed via a hot filtration test.
- Nikoorazm, Mohsen,Khanmoradi, Maryam,Abdi, Zahra
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p. 2577 - 2585
(2020/06/03)
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- Promising new catalytic properties of a Co (II)-carboxamide complex and its derived Co3O4 nanoparticles for the Mizoroki-Heck and the Epoxidation reactions
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The new Co(II) - carboxamide complex (1) and Co3O4 nanoparticles (2), by way of thermal decomposition of (1) have been efficiently synthesised in the environment-friendly. X-ray diffraction reveals a slightly distorted octahedral coordination of cobalt (four nitrogens and two oxygens) in (1) and regular octahedral or tetrahedral ones (oxygens only) in (2). The investigation of (1) and (2) in the Mizoroki-Heck and epoxidation of alkens reactions showed them both to be powerful, green and inexpensive catalysts.
- Kiani, Mahsa,Bagherzadeh, Mojtaba,Meghdadi, Soraia,Fadaei-Tirani, Farzaneh,Babaie, Maryam,Schenk-Jo?, Kurt
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- Linear o-phenanthroline compound and preparation method and application thereof
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The invention belongs to the field of catalytic chemistry, and particularly relates to a linear o-phenanthroline compound and a preparation method and application thereof. The preparation method of alinear o-phenanthroline bidentate nitrogen ligand as sho
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Paragraph 0039-0044
(2020/05/14)
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- Preparation method of phenyl acrylate compound under palladium catalysis
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The invention relates to a preparation method of an aryl acrylate derivative under palladium catalysis. The structural formula of the prepared aryl acrylate compound is shown as figure 1, wherein R ismethyl, ethyl or tert-butyl. The preparation method comprises the following steps of: reacting sodium benzenesulfinate, an acrylate compound, bis(triphenylphosphine)palladium chloride, silver hexafluoroantimonate and copper acetate monohydrate at 60DEG C for 12 hours by using toluene as a solvent, performing extracting with an organic solvent, and conducting concentrating and purifying to obtainthe phenyl acrylate compound. The method has the characteristics of easily available raw materials, mild reaction conditions, simple operation, good repeatability and the like.
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Paragraph 0004
(2020/11/09)
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- Air-Stable Fe3O4@SiO2-EDTA-Ni(0) as an Efficient Recyclable Magnetic Nanocatalyst for Effective Suzuki-Miyaura and Heck Cross-Coupling via Aryl Sulfamates and Carbamates
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The synthesis of inexpensive and novel air-stable Ni(0) nanoparticles immobilized on the EDTA-modified Fe3O4@SiO2 nanocatalyst was investigated in Suzuki-Miyaura and Heck cross-coupling reactions. This catalytic system displayed a greatly improved substrate scope for the carbon–carbon bond formations starting from a wide range of green and economical electrophiles aryl and heteroaryl carbamates and sulfamates via highly efficient method under mild, operationally simple reaction conditions. The synthesized heterogeneous catalyst was also fully characterized by FT-IR, TEM, XRD, DLS, FE-SEM, UV–Vis, EDX, XPS, TGA, NMR, VSM, ICP and elemental analysis techniques. The heterogeneous magnetic nanocatalyst can easily be recovered by an external magnetic field and reused for the next reactions for at least seven times with negligible leaching of catalyst and no substantial decrement in the activity. All these highlights have made the present protocol an interesting, simple and environmentally benign process with low catalyst loading and easy manipulations.
- Dindarloo Inaloo, Iman,Majnooni, Sahar,Eslahi, Hassan,Esmaeilpour, Mohsen
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- Threonine stabilizer-controlled well-dispersed small palladium nanoparticles on modified magnetic nanocatalyst for Heck cross-coupling process in water
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We report the synthesis of magnetically separable Fe3O4@Silica-Threonine-Pd0 magnetic nanoparticles with a core–shell structure. After synthesis of Fe3O4@Silica, threonine as an efficient stabilizer/ligand was bonded to the surface of Fe3O4@Silica. Then, palladium nanoparticles were generated on the threonine-modified catalyst. The threonine stabilizer helps to generate palladium nanoparticles of small size (less than 4?nm) with high dispersity and uniformity. Magnetically separable Fe3O4@Silica-Threonine-Pd0 nanocatalyst was fully characterized using various techniques. This nanocatalyst efficiently catalysed the Heck cross-coupling reaction of a variety of substrates in water medium as a green, safe and inexpensive solvent at 80°C. The Fe3O4@Silica-Threonine-Pd0 catalyst was used for at least eight successful consecutive runs with palladium leaching of only 0.05%.
- Sarvi, Iraj,Gholizadeh, Mostafa,Izadyar, Mohammad
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- Green, cost-effective and efficient procedure for Heck and Sonogashira coupling reactions using palladium nanoparticles supported on functionalized Fe3O4@SiO2 by polyvinyl alcohol as a highly active, durable and reusable catalyst
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A novel heterogenized organometallic catalyst was synthesized by coordinating palladium with polyvinyl alcohol-functionalized Fe3O4@SiO2 nanospheres. This novel catalyst was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscope, field emission scanning electron microscope, dynamic light scattering, UV–vis spectroscopy, X-ray photoelectron spectroscopy, energy dispersive X-ray analysis, thermogravimetric analysis and inductively coupled plasma analysis. The prepared palladium nanoparticles supported on polyvinyl alcohol functionalized Fe3O4@SiO2 nanoparticles were successfully applied as a magnetically recyclable catalyst in Heck and Sonogashira coupling reactions in water. They showed remarkable activity toward aryl halides (I, Br, Cl) using very low palladium loading in excellent yields and demonstrated high TONs (mmol of product per mmol of catalyst). Also, the catalyst could be magnetically separated and reused seven times without any appreciable loss of catalytic activity.
- Sardarian, Ali Reza,Eslahi, Hassan,Esmaeilpour, Mohsen
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- Boehmite@tryptophan-Pd nanoparticles: A new catalyst for C–C bond formation
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A boehmite@tryptophan-Pd nanoparticulate catalyst was prepared by a simple, fast and convenient route. The nanomaterial was characterized using various techniques and employed as a thermally stable catalyst for Heck, Stille and Suzuki cross-coupling reactions. Optimized conditions for these reactions are described. The catalyst could be isolated, post-reaction, by simple filtration and recycled for several consecutive cycles without a notable change in its activity.
- Ghorbani-Choghamarani, Arash,Mohammadi, Masoud,Hudson, Robert H.E.,Tamoradi, Taiebeh
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- Synthesis and characterization of γ-Fe2O3@SiO2-(CH2)3-PDTC-Pd magnetic nanoparticles: A new and highly active catalyst for the Heck/Sonogashira coupling reactions
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In this research, the synthesis and characterization of a novel catalyst is reported based on the preparation of the Pd complex of (pyridin-2-ylmethyl)dithiocarbamate (PDTC) supported on γ-Fe2O3@SiO2 magnetic nanoparticles (γ-Fe2O3@SiO2-(CH2)3-PDTC-Pd). The catalyst is characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, inductively coupled plasma analysis, X-ray powder diffraction, X-ray photoelectron spectroscopy, and vibrating-sample magnetometer measurements. The catalytic performance of γ-Fe2O3@SiO2-(CH2)3-PDTC-Pd was evaluated in the Heck/Sonogashira coupling reactions of various aryl halides with various alkenes/phenylacetylene in water. The synthesized nanocatalyst showed a high catalytic activity even in very small amounts (5 mg, less than 0.1 mol%), was easily separated using magnetic decantation and was reused for ten cycles without any appreciable loss of its reactivity.
- Tashrifi, Zahra,Bahadorikhalili, Saeed,Lijan, Hossein,Ansari, Samira,Hamedifar, Haleh,Mahdavi, Mohammad
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p. 8930 - 8938
(2019/06/17)
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- Palladium nanoparticles immobilized on EDTA-modified Fe3O4@SiO2: a highly stable and efficient magnetically recoverable catalyst for the Heck–Mizoroki coupling reactions
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Palladium nanoparticles supported on EDTA-modified Fe3O4@SiO2 NPs as an efficient and magnetically reusable nanocatalyst was applied for the Heck cross-coupling reactions. The catalyst was very effective for the Heck reaction of aryl halides (iodides, bromides, and chlorides) with alkenes and conversion was excellent in most cases with higher TOF (turn over frequency). Moreover, the catalyst could be recycled for eight runs without any significant loss of catalytic activity, showing its superiority over homogeneous catalysts for industrial and chemical applications. Also, the leaching of the catalyst has been examined by a hot filtration test and ICP analysis.
- Esmaeilpour, Mohsen,Zahmatkesh, Saeed
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p. 267 - 276
(2019/09/13)
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- Bis-salophen palladium complex immobilized on Fe3O4@SiO2 nanoparticles as a highly active and durable phosphine-free catalyst for Heck and copper-free Sonogashira coupling reactions
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New Fe3O4@SiO2 core-shell superparamagnetic nanoparticles functionalized by a bis-salophen Schiff base Pd complex were synthesized and employed as an efficient magnetic nanocatalyst in the Heck and Sonogashira cross coupling reactions. The synthesized nanostructures were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), dynamic light scattering (DLS), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), elemental analysis (CHN), cyclic voltammetry (CV), Brunauer-Emmett-Teller analysis (BET), and UV-vis spectroscopy. The morphology and size of the nanoparticles were investigated by FE-SEM and TEM analyses. Furthermore, the magnetic properties of the catalyst were investigated by VSM analysis. The loading content and leaching amounts of palladium on the catalyst were measured by inductively coupled plasma (ICP) analysis. Also, the thermal behavior of this magnetic heterogeneous catalyst was studied using a TGA instrument. This heterogeneous catalytic system showed a good performance in the coupling of aryl halides with alkynes (Sonogashira reaction) as well as aryl halides with alkene derivatives (Heck reaction). High to excellent yields were achieved for these C-C coupling reactions. The catalyst can be simply separated from the reaction media by an external magnet and reused for eight consecutive runs without any significant loss of activity. Finally, the kinetics of the reactions were studied in this work.
- Sardarian, Ali Reza,Kazemnejadi, Milad,Esmaeilpour, Mohsen
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p. 3132 - 3145
(2019/03/06)
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- Ultra-small and highly dispersed Pd nanoparticles inside the pores of ZIF-8: Sustainable approach to waste-minimized Mizoroki–Heck cross-coupling reaction based on reusable heterogeneous catalyst
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The rapid development of nanomaterials, particularly advanced hybrid nanoparticles, has made new opportunities for the design and fabrication of high-performance metal-based catalysts. However, generating metal nanoparticles of desired size without aggregation is an important challenge for enhancing the catalytic activity of metal nanoparticles supported in the host matrix. In this work, a hybrid nanoporous material, namely Pd nanoparticles@N-heterocyclic carbene@ZIF-8, with a high internal surface area was successfully prepared using a dispersed anionic sulfonated N-heterocyclic carbene–Pd(II) precursor inside the cavities of zeolitic imidazolate framework (ZIF-8) using an impregnation approach followed by reduction with NaBH4. The anionic sulfonated N-heterocyclic carbene was found to be a superb ligand for the stabilization of Pd nanoparticles in the pores of ZIF-8. The resulting system was applied to the Mizoroki–Heck cross-coupling reaction, in which the catalyst showed high catalytic activity under mild reaction conditions.
- Azad, Mohammad,Rostamizadeh, Shahnaz,Estiri, Hamid,Nouri, Fatemeh
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- Imidazolium chloride-Co(iii) complex immobilized on Fe3O4@SiO2 as a highly active bifunctional nanocatalyst for the copper-, phosphine-, and base-free Heck and Sonogashira reactions
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A heterogeneous, magnetically recoverable Fe3O4@SiO2@Im[Cl]Co(iii)-melamine nanocomposite was prepared by immobilization of a novel Co(iii) Schiff base complex on Fe3O4@SiO2 nanoparticles followed by treatment with melamine, and was found to be an efficient catalyst for the Heck and Sonogashira reactions. The reactions were performed in the presence of the catalyst (0.5 mol% Co) along with Mn additive in the absence of any base, phosphine ligand, or Cu/co-catalyst in ethanol under reflux conditions. The nanocatalyst was well studied by FTIR, CHN, XRD, XPS, TGA, EDX, VSM, ICP, NMR, FE-SEM, TEM, BET, CV, and DLS analyses. The catalyst was compatible with a variety of substrates, with which all the Heck and Sonogashira coupling products were obtained in high to excellent yields. Also, protocols such as hot filtration, three-phase testing, and mercury poisoning provided a complete insight into the nature of the heterogeneous catalyst. The recycling and reuse of the catalyst were studied for both coupling reactions several times. Moreover, the mechanism of the coupling reactions was entirely investigated.
- Kazemnejadi, Milad,Alavi, Seyyedeh Ameneh G.,Rezazadeh, Zinat,Nasseri, Mohammad Ali,Allahresani, Ali,Esmaeilpour, Mohsen
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p. 1718 - 1734
(2019/04/08)
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- Cobalt supported on dendronized magnetic nanoparticles: A new highly efficient and recyclable catalyst for the Mizoroki–Heck cross-coupling reaction
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Polyamidoamine (PAMAM) is one of the most interesting types of hyperbranched polymers that carry a large number of amino groups on its surface. PAMAM has gained significant attention from synthetic organic chemists due to its structural characteristics, controllable structure, inner porosity, and ability to trap a wide range of ions and molecules. So, in this work, the PAMAM dendrimer was synthesized, grafted onto the surface of magnetite nanoparticles, and the resulting hybrid nanoparticles were then employed as suitable host for immobilizing cobalt nanoparticles. The newly developed catalyst was well characterized by Fourier transform-infrared, X-ray diffraction, thermogravimetric analysis, field emission-scanning electron microscopy, transmission electron microscopy, atomic absorption spectroscopy, element mapping and energy-dispersive X-ray analysis. The efficiency of the as-prepared nanocatalyst was evaluated for the Mizoroki–Heck cross-coupling reactions. The MNP@PAMAM-Co represented perfect catalytic efficiency and high selectivity for the Mizoroki–Heck cross-coupling reaction compared with previously reported catalysts. The catalyst separation from the reaction mixture was easily achieved with the assistance of an external magnetic field, and its recycling was also investigated for five consecutive runs. Hot filtration confirmed no leaching of the active metal during the Heck coupling.
- Arghan, Maryam,Koukabi, Nadiya,Kolvari, Eskandar
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- Magnetic apple seed starch functionalized with 2,2′-furil as a green host for cobalt nanoparticles: Highly active and reusable catalyst for Mizoroki–Heck and the Suzuki–Miyaura reactions
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From the perspective of green chemistry, in catalytic systems, being low cost and eco-friendly, in addition to high chemical and thermal stability, are requirements of support materials. In this regard, we used apple seed starch as an accessible, nontoxic, and cost-effective support material. In order to take advantage of magnetic separation, the magnetite nanoparticles were chosen as an ideal pair for apple seed starch. Furthermore, during the Schiff base reaction, the magnetic apple seed starch was functionalized with 2,2′-furil along with amine functionality to be used as a bio-support for immobilization of cobalt. The introduction of cobalt had a significant effect on the greenness of the catalyst and reducing its price. FT-IR, TGA, XRD, FE-SEM, TEM, VSM, ninhydrin test, element mapping, AAS, and EDX analysis were applied to characterize the newly prepared catalyst. The effectiveness of this novel Schiff base supported catalyst was evaluated in the Mizoroki–Heck and the Suzuki–Miyaura coupling reactions. High reactivity and selectivity were among the most prominent characteristics of the catalyst as compared to previously reported catalysts. The longevity test and hot filtration showed the ability to use the catalyst at least 5 times and negligible cobalt leaching during the reaction, respectively. This work is the first report on the usage of apple seed starch as a supporting catalyst and 2,2′-furil as a ligand in the catalyst modifications and catalytic activity. Accordingly, this can be the beginning of an attractive way in the design and synthesis of heterogeneous catalysts.
- Arghan, Maryam,Koukabi, Nadiya,Kolvari, Eskandar
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- PdII Immobilized on Ferromagnetic Multi-Walled Carbon Nanotubes Functionalized by Aminated 2-Chloroethylphosphonic Acid with S -Methylisothiourea (FMMWCNTs@CPA@SMTU@PdII NPs) Applied as a Highly Efficient and Recyclable Nanostructured Catalyst for Suzuki-Miyaura and Mizoroki-Heck Cross-Coupling Reactions in Solvent-Free Conditions
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The new ferromagnetic nanostructured FMMWCNTs@CPA@SMTU@PdII NPs (IV) as an eco-friendly heterogeneous nanocatalyst with a particle size of ~20-30 nm reported earlier by our group has been found to be very effective for Suzuki-Miyaura and Mizoroki-Heck cross-coupling reactions at ambient temperature. The procedure has been applied for a wide range of aryl halides, arylboronic acids, and alkenes. The magnetic separation by an external magnetic field, mild reaction conditions, and catalyst reusability up to four times without significant decrease in catalytic activity (reduced catalytic activity from 11 to 18 % in the fifth, sixth, and seventh cycles) made the present method sustainable and economically viable for C-C cross-coupling reactions.
- Ghasemzadeh, Maryam Sadat,Akhlaghinia, Batool
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p. 674 - 692
(2019/07/12)
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- Palladium(ii) ligated with a selenated (Se, CNHC, N-)-type pincer ligand: An efficient catalyst for Mizoroki-Heck and Suzuki-Miyaura coupling in water
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A new 1-[N-benzylacetamido]-3-[1-(2-phenylselenylethyl)]benzimidazolium chloride (L), the precursor of a novel (Se, CNHC, N-)-type pincer ligand (L) was synthesised in high yield through a sequence of consecutive reactions of 1H-benzimidazole with ethylene dichloride, sodium selenophenolate, and N-benzyl-2-chloroacetamide. The palladium-promoted reaction of L with PdCl2 resulted in a moisture- and air-insensitive complex [Pd(L-H2Cl)Cl] (1), which demonstrated outstanding catalytic potential for Mizoroki-Heck coupling of aromatic bromides and chlorides (with yields up to 94% and 70%, respectively) at very low catalyst loading (0.2 mol%) and under mild reaction conditions in water. The complex (1) was also investigated for Suzuki-Miyaura coupling and found to be selectively efficient (yields up to 94%) for Suzuki-Miyaura coupling of aromatic bromides at 0.01 mol% of 1 in water. All coupling reactions were carried out in the green and economical solvent, water, which is highly desirable for bulk synthesis of complex molecules in industry. During the catalytic process, complex 1 converted into PdSe nanoparticles (NPs, size range 5-6 nm) in situ. The morphology and composition of these NPs were analysed through high-resolution transmission electron microscopy and transmission electron microscopy-energy dispersive X-ray spectroscopy, respectively. The core-level, X-ray photoelectron spectroscopy analysis confirmed the presence of stable Pd0 and Pd2+ oxidation states in these PdSe NPs. Based on further experimental investigations, these nanoparticles were found to work as a stock of true catalytic species. The hot filtration test, as well as the two-phase test, confirmed the largely homogeneous nature of the catalytic process, which probably proceeds by leaching of solution-phase Pd species from these NPs.
- Sharma, Kamal Nayan,Satrawala, Naveen,Srivastava, Avinash Kumar,Ali, Munsaf,Joshi, Raj Kumar
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p. 8969 - 8976
(2019/10/28)
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