- A palladium-loaded mesoporous polymer monolith as reusable heterogeneous catalyst for cross-coupling reactions
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A new palladium catalyst based on a mesoporous polymer monolith has been introduced. A polyacrylonitrile (PAN) monolith prepared by a phase separation technique was used as precursor material for chemical modification; the nitrile groups on the monolith surface were transformed into amidine groups and then bound to palladium dichloride via coordination. A series of Suzuki-Miyaura cross-coupling reactions were successfully demonstrated by using the monolith as catalyst. Moreover, the monolith was found to exhibit excellent stability for repeated use.
- Kundu, Dhiman,Patra, Astam K.,Sakamoto, Junji,Uyama, Hiroshi
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- Guanidine/Pd(OAc)2-catalyzed room temperature Suzuki cross-coupling reaction in aqueous media under aerobic conditions
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(Chemical Equation Presented) A highly efficient Pd(OAc) 2/guanidine aqueous system for the room temperature Suzuki cross-coupling reaction has been developed. The new water-soluble and air-stable catalyst Pd(OAc)2·(1f)2 from Pd-(OAc)2 and 1,1,3,3-tetramethyl-2-n-butylguanidine (1f) was synthesized and characterized by X-ray crystallography. In the presence of Pd(OAc) 2·(1f)2, coupling of arylboronic acids with a wide range of aryl halides, including aryl iodides, aryl bromides, even activated aryl chlorides, was carried out smoothly in aqueous solvent to afford the cross-coupling products in good to excellent yields and high turnover numbers (TONs) (TONs up to 850 000 for the reaction of 1-iodo-4-nitrobenzene and phenylboronic acid). Furthermore, this mild protocol could tolerate a broad range of functional groups.
- Li, Shenghai,Lin, Yingjie,Cao, Jungang,Zhang, Suobo
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- Highly active, durable and recyclable ordered mesoporous magnetic organometallic catalysts for promoting organic reactions in water
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A new strategy of bonding organometallics to an MCM-41 thin layer coated onto Fe3O4 microspheres with strong magnetism, denoted as M-PPh2-MCM-41@SiO2@Fe3O4, where M = Pd(ii) and Rh(i), has been developed for the immobilization of homogeneous catalysts. In comparison with the traditional M-PPh2-MCM-41 catalysts with irregular shapes and the M-PPh2-SiO2@Fe 3O4 without an ordered mesoporous structure, the current catalysts exhibited much higher activities for various water-based Suzuki, Sonogashira and Miyaura-Michael organic reactions, due to the high dispersion of active sites and the uniform catalyst particles with short-ordered mesopores favoring reactant diffusion and adsorption. Their catalytic efficiencies are comparable with those of the homogeneous catalysts, and they could be easily recycled for reuse by simply applying an external magnet.
- Zhang, Fang,Chen, Mingzhen,Wu, Xiaotao,Wang, Wei,Li, Hexing
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- An efficient and reusable catalyst based on Pd/CeO2 for the room temperature aerobic Suzuki-Miyaura reaction in water/ethanol
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The Pd/CeO2 system behaves as an efficient precatalyst for the Suzuki-Miyaura cross-coupling under mild conditions (298 K, in air) in ethanol/water. A broad range of aryl bromides, including those deactivated, and arylboronic acids underwent Suzuki-Miyaura coupling with quantitative GC yields of asymmetric biaryls. Isolated yields and purity of the coupling products were good to excellent. A careful investigation through a series of suitable tests unequivocally showed that the C-C cross-coupling is accomplished via homogeneous mechanism by leached palladium(0). Noticeably, the Pd/CeO2 system can be recycled at least ten times without loss of activity.
- Amoroso, Francesco,Colussi, Sara,Del Zotto, Alessandro,Llorca, Jordi,Trovarelli, Alessandro
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- Stille-type aryl-aryl cross-coupling catalysis using triarylphosphine ligands with electron-rich Fe(ii)-alkynyl substituents
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The synthesis of four new phosphane ligands featuring electron-rich Fe(ii) "(η2-dppe)(η5-C5Me 5)FeCC-" substituents in para and meta position(s) on the aryl rings (1-4) is reported along with those of the corresponding PdCl 2(PAr3)2 precatalysts (7-10). These precatalysts have then been tested in a Stille-type aryl-aryl cross coupling reaction. It is shown that these new ligands survive the reaction conditions and perform at least as well as the classic triphenylphosphine ligand for this transformation.
- Grelaud, Guillaume,Tohme, Ayham,Argouarch, Gilles,Roisnel, Thierry,Paul, Frederic
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- Studies on the catalytic ability of palladium wire, foil and sponge in the Suzuki-Miyaura cross-coupling
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Different forms of metallic palladium (wire, foil and sponge) have been tested as potential catalysts in the Suzuki-Miyaura cross-coupling. All samples showed to be catalytically active for both electron-poor and electron-rich aryl bromides combined with a variety of arylboronic acids. Palladium wire has been recycled six times without decrease of activity. A series of poisoning experiments demonstrated that the true catalyst is a soluble form of palladium arising from a leaching process. Interestingly, metal leaching from palladium foil has been clearly evidenced by SEM.
- Amoroso, Francesco,Cersosimo, Ulma,Del Zotto, Alessandro
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- Facile Synthesis of Magnetic Hierarchical Core–Shell Structured Fe3O4@PDA-Pd@MOF Nanocomposites: Highly Integrated Multifunctional Catalysts
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A magnetic hierarchical core–shell structured Fe3O4@PDA-Pd@[Cu3(btc)2] nanocomposite has been fabricated via a facile layer-by-layer assembly method. It contains a core of polydopamine (PDA)-modified magnetic Fe3O4 nanoparticles (NPs), a transition layer of Pd NPs, and a porous outer shell of copper-based metal–organic framework (MOF) with controllable thickness. This novel nanocomposite was characterized by TEM, FTIR, XRD, XPS, N2 adsorption–desorption isotherms, and VSM. The prepared Fe3O4@PDA-Pd@[Cu3(btc)2] (n=5) nanocomposite shows ultrahigh catalytic activity for the 4-nitrophenol reduction and Suzuki–Miyaura coupling reactions of aryl halides (Br, Cl) with arylboronic acids. Moreover, the nanocomposite also can be easily separated by an external magnet and reused at least 8 runs with excellent yields for both the reactions. The catalyst has outstanding catalytic performance, mainly because the integration of [Cu3(btc)2] with Fe3O4@PDA-Pd that combines the advantages of each component could exhibit a synergistic effect in the catalytic system.
- Ma, Rong,Yang, Pengbo,Ma, Yao,Bian, Fengling
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- Enhancing activity of Suzuki reactions in water by using guanidinium ionic liquid stabilized palladium micelle catalyst
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A facile surfactant-based hexaalkylguanidinium ionic liquid (GIL)-mediated Suzuki coupling procedure has been developed using ligand-free Pd catalysts. The procedure involving the use of nanometric palladium micelles, is operationally simple and remarkably efficient for the coupling of aryl bromides or aryl chlorides with boronic acids in water. Furthermore, the GIL/H2O catalytic system was more stable than the tetrabutylammonium bromide/H 2O catalytic system under basic conditions, enabling the recycling of the nano-Pd micelle catalysts. Georg Thieme Verlag Stuttgart · New York.
- Lin, Li,Li, Yanchun,Zhang, Suobo,Li, Shenghai
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- C–Hortho?Pd interactions in palladium complexes derived from tetrasulfur-difluorinated ligands. Experimental, computational and catalytic studies
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The symmetric ligands [Ar-S-CH2-Ph-S-(CH2)-]2, L1 (Ar = o-FPh) and L2 (Ar = p-FPh), and their PdII complexes (1 and 2) were synthesized and structurally characterized. Molecular structures of complexes 1 and 2 display the L1 and L2 ligands coordinating palladium in a κ2-SS bidentate fashion. The metal center exhibits a square planar geometry involving the two sulfur atoms and two chloride atoms which are oriented in cis disposition. Interestingly, the two ortho-hydrogen atoms from the phenyl rings in both complexes are engaged in Pd?Hortho interactions with distances from 2.976 to 3.280 ?. These distances can suffer an increase or decrease in their longitude due to the presence of intramolecular C–H?π interactions. Additionally, the presence of Pd?H interactions in palladium complexes (1 and 2) were identified by an NCI analysis. The complexes 1, 2 and a similar complex 3 that also displays Pd?Hortho interactions have been evaluated in the Suzuki-Miyaura cross-coupling reactions.
- González-Montiel, Simplicio,Sandoval-Chávez, César Ignacio,Mu?oz-Granados, Oscar,Martínez-Otero, Diego,Vásquez-Pérez, J. Manuel,Cruz-Borbolla, Julián,Velázquez-Jiménez, René,López, Jorge A.
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- Synthesis and catalytic activity of cationic dinuclear palladium (II) complexes supported by thioether ligands containing two di-(2-picolyl) amine arms
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The design, synthesis and characterization of a series of dithioether ligands featuring two di-(2-picolyl)amine arms (2a–2d) and their corresponding cationic dinuclear palladium (II) complexes (3a–d) are reported. Crystal structures of ligand 2b and complexes 3b and 3d were determined by X-ray diffraction studies. The molecular structures of 3b and 3d display each of the two di-(2-picolyl)amine fragments coordinated to one palladium(II) atom in a (κ3-N,N,N) tridentate fashion and with the cationic metal centers displaying square-planar geometries. Weak interactions between the metal centers and the thioether fragments are observed. All bimetallic complexes 3a–d were tested as catalytic precursors in the Suzuki couplings of different o- or p-substituted iodo- or bromoaryls with boronic acids. The overall catalytic results indicate that complex 3b is the best precursor of the series demonstrating even more efficient performance compared to commercial palladium sources such as Pd(OAc)2 and the Nájera Catalysts.
- Andrade-López, Noemi,González-Montiel, Simplicio,Martínez-Otero, Diego,Salazar-Pereda, Verónica,Sandoval-Chávez, César Ignacio,Velázquez-Jiménez, René
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- Cooperative effects of lanthanides when associated with palladium in novel, 3D Pd/Ln coordination polymers. Sustainable applications as water-stable, heterogeneous catalysts in carbon-carbon cross-coupling reactions
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Three novel porous heterobimetallic coordination polymers, [Ln2Pd3(BPDC)2(HBPDC)2(μ2-O)Cl4(H2O)6·nH2O]m (Ln = Pr, n = 5 (1), Ln = Gd, n = 4 (2), and Ln = Tb, n = 4 (3)), were readily prepared by combining Pd(II) and Ln(III) with 2,2′-bipyridine-4,4′-dicarboxylic acid (H2BPDC) as a heteroleptic ligand, under hydrothermal conditions, and structurally characterized by means of single-crystal X-ray diffraction, FT-IR, powder X-ray diffraction, elemental analysis and thermogravimetric (TG) techniques. Single-crystal X-ray diffraction examination showed that 1-3 have similar 3D frameworks, connected via hydrogen bonding interactions, and consisting of three distinct types of building blocks: Pd(BPDC)Cl2, Pd(HBPDC)2 and a Ln dimer (Ln2O15). The new isostructural, air and water stable coordination polymers, resulting from association of lanthanides with palladium, exhibited superior but distinct capabilities as eco-friendly heterogeneous catalysts in Suzuki-Miyaura, Heck and Sonogashira cross-couplings, under green reaction conditions. Supramolecular, solid catalysts 1-3 have been recovered quantitatively from the reaction mixtures by simple filtration. Also importantly, their sustainability, utility and cost-effectiveness have been demonstrated by recycling experiments with catalyst 1 in Suzuki-Miyaura, proceeding practically without loss of activity after four runs.
- You, Lixin,Zong, Wenhui,Xiong, Gang,Ding, Fu,Wang, Shuju,Ren, Baoyi,Dragutan, Ileana,Dragutan, Valerian,Sun, Yaguang
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- Ionic-liquid-grafted rigid poly (p-Phenylene) microspheres: Efficient heterogeneous media for metal scavenging and catalysis
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Novel guanidinium ionic liquid-grafted rigid poly(p-phenylene) (PPPIL) microspheres have been developed for metal scavenging and catalysis. The noble-metal nanoparticles supported on the microspheres surface can be used as efficient heterogeneous catalysts. The combination of nanoparticles and ionic liquid fragments on the microsphere surfaces enhance the activity and durability of the catalyst. The PPPIL-Pd0 catalyst has been tested in the Suzuki cross-coupling reaction, and exhibits much higher catalytic activity than Pd catalysts supported on porous polymer matrices. The PPPIL-Pd0 catalyst can be recycled at least for nine runs without any significant loss of activity. The present approach may, therefore, have potential applications in transition-metal-nanocatalyzed reactions.
- Li, Shenghai,Wang, Junhua,Kou, Yongli,Zhang, Suobo
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- Iron(0), rhodium(I) and palladium(II) complexes with p-(N,N- dimethylaminophenyl) diphenylphosphine and the application of the palladium complex as a catalyst for the Suzuki-Miyaura cross-coupling reaction
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The reaction of p-(N,N-dimethylaminophenyl)diphenylphosphine [PPh 2(p-C6H4NMe2)] with [Fe 3(CO)12], [Rh(CO)2Cl]2 and PdCl 2 resulted in three new mononuclear complexes, {Fe(CO) 4[I·1-(P)-PPh2(p-C 6H4NMe2)]} (1a), trans-{Rh(CO) Cl[I·1-(P)-PPh2(p-C6H 4NMe2)]2} (2) and trans-{PdCl 2[I·1-(P)-PPh2(p-C 6H4NMe2)]2} (3), respectively. A small amount of dinuclear nonmetal-metal bonded complex, {Fe2(CO) 8[μ-(P,N)-PPh2(p-C6H4NMe 2)]} (1b), was also isolated as a side product in the reaction of [Fe3(CO)12]. The complexes were characterized by elemental analyses, mass, IR, UV-vis, 1H, 13C (except 1b) and 31P{1H} NMR spectroscopy. The Pd complex 3 effectively catalyzes the Suzuki-Miyaura cross-coupling reactions of aryl halides with arylboronic acids in water-isopropanol (1:1) at room temperature. Excellent yields (up to 99% isolated yield) were achieved. The effects of different solvents, bases, catalyst quantities were also evaluated. Copyright
- Sarmah, Chandan,Borah, Malabika,Das, Pankaj
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- Improving the rates of Pd-catalyzed reactions by exciting the surface plasmons of AuPd bimetallic nanotriangles
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Gold nanoparticles exhibit unique optical properties due to surface plasmon oscillations when they interact with light. By utilizing their optical properties, the rates of many chemical reactions have been improved in the presence of visible light. The properties of plasmonic nanoparticles are highly tunable based on the size and shape of the nanoparticle. Here, we have used anisotropic AuPd bimetallic nanotriangles to improve the rates of Pd-catalyzed reactions in the presence of visible light. We synthesized AuPd core-shell bimetallic nanotriangles and performed Suzuki cross-coupling and hydrogenation reactions in light and dark conditions. Upon illuminating AuPd nanotriangles with an array of green LEDs (power ~ 500 mW), enhanced catalytic activity of palladium was observed. In order to understand the relative contributions of individual plasmonic effects, such as plasmonic hot electron transfer and plasmonic heating effects, the reaction temperatures were monitored, and careful control experiments were run at different temperatures. Our results indicated that the enhancement in the rate of these Pd-catalyzed reactions is primarily due to the plasmonic heating effect.
- Gangishetty, Mahesh K.,Fontes, Adriana M.,Malta, Marcos,Kelly, Timothy L.,Scott, Robert W.J.
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- Room-temperature Suzuki-Miyaura reaction catalyzed by Pd supported on rare earth oxides: Influence of the point of zero charge on the catalytic activity
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Five Pd/REO (rare earth oxide) compounds (Pd/La2O3, Pd/CeO2, Pd/Pr6O11, Pd/Sm2O 3, and Pd/Gd2O3) have been successfully used as precatalysts in the Suzuki-Miyaura C-C cross-coupling reaction of aryl bromides with arylboronic acids in ethanol/water at r.t. All Pd/REO showed high activity and selectivity. The effective catalyst arises from palladium leaching from the REO support. We have demonstrated that the activity of each Pd/REO (the decreasing order is Pd/La2O3 > Pd/Pr6O 11 > Pd/Gd2O3 > Pd/Sm2O 3 ? Pd/CeO2) is strictly related to the corresponding PZC (point of zero charge) value. Accordingly, it can be reasonably argued that the metal is released in solution in the form of Pd2+, and higher is the amount of positive charge on the surface in catalytic conditions, higher is the concentration of Pd2+ ions in solution and faster is the formation of the coupling product. Also the recycling of each Pd/REO is strictly connected with the PZC value of the REO support. As a matter of fact, Pd/CeO2, which has the lowest PZC value (6.7), shows the best reusability, according to its lower tendency to release Pd2+ ions in solution.
- Amoroso, Francesco,Colussi, Sara,Del Zotto, Alessandro,Llorca, Jordi,Trovarelli, Alessandro
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- Suzuki-Miyaura reactions of aryl chloride derivatives with arylboronic acids using mesoporous silica-supported aryldicyclohexylphosphine
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The Suzuki-Miyaura reactions using mesoporous-supported aryldicyclohexylphosphine as ligand have been investigated. The catalysts were based on SBA-15 type mesoporous silica which was transformed in a four-step synthesis leading to a phosphine-containing hybrid material The most productive catalytic system studied was generated in situ from this material and the homogeneous palladium complex, Pd(OAc)2. Other catalytic systems were studied for comparison [homogeneous cataysts, a "preformed" catalyst obtained by reaction of PdCl2 (PhCN)2 and the phosphine-containing material]. Variations involving the solvent system, the substrate aryl chloride and the arylboronic acid reactant were also studied. For both in situ and preformed cataiyst systems, high conversions and yields are obtained for activated aryl chlorides. Success of the reaction for unactivated aryl chlorides was limited to the catalyst formed in situ. The catalyst formed in situ was also shown to be reactive under aqueous reaction conditions in the cross-coupling of 1-(4-chlorophenyl)ethanone with phenylboronic acid.
- Sayah, Reine,Glegola, Katarzyna,Framery, Eric,Dufaud, Veronique
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- Palladium(II) complex with a potential N4-type Schiff-base ligand as highly efficient catalyst for Suzuki-Miyaura reactions in aqueous media
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Two new air-stable palladium(II) complexes containing a N 4-Schiff-base ligand have been synthesized and investigated as catalysts for the Suzuki-Miyaura reactions. The binuclear complex 2 has proven to be an excellent catalyst for additive-free Suzuki-Miyaura reactions of aryl bromides in neat water at room temperature and aryl chlorides in aqueous-glycerol at 80 °C. Satisfactory to excellent yields of biaryls are obtained with a wide range of substrates with relatively low loading of catalyst.
- Banik, Biplab,Tairai, Archana,Shahnaz, Nasifa,Das, Pankaj
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- Simple mixed tricyclohexylphosphane-triarylphosphite complexes as extremely high-activity catalysts for the Suzuki coupling of aryl chlorides
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The most active catalyst yet reported for the Suzuki coupling of activated aryl chlorides, even for electronically deactivated substrates, is generated by addition of tricyclohexylphosphane to the otherwise inactive orthopalladated complex 1 [Eq. (1); for
- Bedford, Robin B.,Cazin, Catherine S. J.,Hazelwood, Samantha L.
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- PEG350-based di-(2-pyridyl)methylamine as a ligand in the Pd-catalyzed water Suzuki-Miyaura reaction of aryl chlorides
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The synthesis of new hydrosoluble PEG-based ligand derived from di-(2-pyridyl)methylamine has been developed. The catalytic performance of this ligand is demonstrated in Suzuki-Miyaura reactions between aryl chlorides and arylboronic acids and using water as solvent.
- Adidou, Ouissam,Goux-Henry, Catherine,Safi, Mohamed,Soufiaoui, Mohamed,Framery, Eric
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- Palladium on carbon-catalyzed cross-coupling of aryl halides with potassium p-tolyltrifluoroborate in air
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Palladium supported on carbon (Pd/C) has been shown to be an effective catalyst for the cross-coupling of potassium p-tolyltrifluoroborate with a variety of aryl bromides and iodides. Yields ranging from moderate to good were obtained using Pd/C in ethano
- LeBlond, Carl R.,Butler, Kaycie M.,Ferrington, Marc W.,Browe, Matthew A.
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- Pseudo-Solid-State Suzuki–Miyaura Reaction and the Role of Water Formed by Dehydration of Arylboronic Acids
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Solvent-free reactions belong to a very attractive area of organic chemistry. The solvent-free Suzuki–Miyaura coupling is of special importance due to the problem of catalyst leaching in the presence of a solvent. This study investigates the course of reaction of solid aryl halides with arylboronic acids in the absence of a solvent and without any liquid additives. For the first time, a number of important conditions for performing a solid-state Suzuki–Miyaura reaction were analyzed in details. The results indicate a prominent role of water, which is formed as a by-product in the side reaction of arylboronic acid trimerization. Electron microscopy study revealed surprising changes occurring within the reaction mixture during the reaction and indicated the formation of spherical nano-sized particles containing the reaction product. Catalyst recycling was easily performed in the developed system and the product was isolated by sublimation, thus providing a possibility to completely avoid the use of solvents at all stages.
- Pentsak, Evgeniy O.,Ananikov, Valentine P.
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- Anchoring of palladium (II) in functionalized SBA-16: An efficient heterogeneous catalyst for Suzuki coupling reaction
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A new functionalized SBA-16 catalyst immobilized palladium (II) has been synthesized. Inductively coupled plasma (ICP), small-angle X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen physical adsorption and Fourier transform infrared (FTIR) studies have been used to characterize the catalyst. The catalyst exhibited very high activity for Suzuki coupling reaction of aryl halides with arylboronic acids in EtOH/water under air atmosphere. On the other hand, the synthesized catalyst could be separated from the reaction mixture by simple filtration and reused up to five runs without significant loss in activity.
- Wei, Shuoyun,Ma, Zongyan,Wang, Peng,Dong, Zhengping,Ma, Jiantai
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- Synthesis and characterization of palladium nanoparticles immobilized on graphene oxide functionalized with triethylenetetramine or 2,6-diaminopyridine and application for the Suzuki cross-coupling reaction
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Graphene oxide (GO) was functionalized with two organic ligands, triethylenetetramine (TETA) or 2,6-diaminopyridine (DAP), followed by palladium nanoparticles (Pd NPs) for the synthesis of Pd NPs/GO-TETA and Pd NPs/GO-DAP nanocomposites, respectively. The two heterogeneous nanocomposites were fully characterized and their efficiency was investigated for C[sbnd]C bond formation for the synthesis of biaryl compounds via the Suzuki cross-coupling reaction of aryl halides with arylboronic acid derivatives. The obtained results indicated that the Pd NPs/GO-TETA nanocomposite was more effective in the Suzuki coupling reaction as compared to Pd NPs/GO-DAP. Thus, the Suzuki cross-coupling reaction of different aryl halides with arylboronic acid derivatives using Pd NPs/GO-TETA nanocomposite catalyst in the presence of Na2CO3 as base in DMF/H2O (1/1) as solvent at 90 °C was carried out to afford the desired biaryl compounds in high to excellent yields (81–100%) and short reaction times (10–90 min). Additionally, Pd NPs/GO-TETA nanocomposite can be recovered and reused for 8 consecutive runs without any apparent loss of its catalytic activity, proving its high stability and potential use in organic transformations.
- Mirza-Aghayan, Maryam,Mohammadi, Marzieh,Boukherroub, Rabah
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- Suzuki-Miyaura Cross-Coupling Reaction with Potassium Aryltrifluoroborate in Pure Water Using Recyclable Nanoparticle Catalyst
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This paper describes the Suzuki Miyaura cross-coupling reaction of aryl bromides with potassium aryltrifluoroborates in water catalyzed by linear polystyrene-stabilized PdO nanoparticles (PSPdONPs). The reaction of aryl bromides having electron-withdrawing groups or electron-donating groups took place smoothly to give the corresponding coupling product in high yields. The catalyst recycles five times without significant loss of catalytic activity although a little bit increase in size of PdNPs was observed after the reaction.
- Kawase, Misa,Matsuoka, Kyosuke,Shinagawa, Tsutomu,Hamasaka, Go,Uozumi, Yasuhiro,Shimomura, Osamu,Ohtaka, Atsushi
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- Biaryl Coupling of Aryldiazonium Salts and Arylboronic Acids Catalysed by Gold
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A gold-catalysed coupling of aryldiazonium salts with arylboronic acids is described. The reactions proceed in satisfactory yields under irradiation with blue LEDs in the presence of KF and a catalytic amount of ascorbic acid. Notably, 4-nitrobenzendiazonium tetrafluoroborate is sufficiently reactive to undergo the coupling with a variety of arylboronic acids in the absence of aryl radical initiators. The coupling is applicable for electron-donating and electron-withdrawing groups present at the para, ortho, and meta positions of both substrates.
- Medina-Mercado, Ignacio,Porcel, Susana
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- Palladium-catalyzed aryl group transfer from triarylphosphines to arylboronic acids
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A study of Pd-catalyzed arylation of arylboronic acids with triarylphosphines is presented. Various parameters of this transformation, such as the oxygen presence, choice of solvent, temperature, palladium source, bases and oxidants, were tested and the optimal conditions of the aryl transfer were determined. The effect of electron-withdrawing and electron-donating substituents on the aryl groups of both reactants was also investigated. The unusual transfer of the acetate group from Pd(OAc)2 to p-nitrophenylboronic acid in the presence of PAr3 is reported. A plausible mechanism of the Pd-catalyzed aryl group transfer from PAr3 to the arylboronic acid is proposed.
- Enright, Dale R.,Gogate, Akash R.,Smoliakova, Irina P.,Vasireddy, Purna C. R.
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- Anchored Pd(0) Nanoparticles on Synthetic Talc for the Synthesis of Biaryls and a Precursor of Angiotensin II Inhibitors
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The palladium-catalyzed Suzuki-Miyaura cross-coupling reaction is one of the most important and efficient reactions to prepare a variety of organic compounds, including biaryls. Despite the overwhelming number of reports related to this topic, some methodological difficulties persist in terms of catalyst handling, recovery, and reuse, as well as the reaction media. This work reports the rational design of new, efficient, cost-effective, and reusable palladium catalysts supported on synthetic talc for the Suzuki-Miyaura reaction. From the results, key points were identified: both designed catalysts accelerated the reaction in EtOH and an open-flask setup, affording moderate to excellent yields within a short time (e.g., 30 min) even for deactivated aryl halides; the protocol can be applied to a great number of both cross-coupling partners, showing an excellent functional group tolerance; the catalysts can be recovered and reused without significant loss of activity. This protocol was used for the synthesis of a precursor of angiotensin II inhibitors such as valsartan, losartan, irbesartan, and telmisartan.
- Dos Santos, Beatriz F.,Da Silva, Beatriz A. L.,De Oliveira, Aline R.,Sarragiotto, Maria H.,Domingues, Nelson Luís C.
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p. 933 - 942
(2020/12/28)
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- Magnetic covalently immobilized nickel complex: A new and efficient method for the Suzuki cross-coupling reaction
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In this study, an efficient procedure was reported to prepare Fe3O4@SiO2 magnetic nanoparticles (MNPs) with immobilized nickel NPs. In order to increase the activity of this catalyst, creatine as a ligand with high content of nitrogen atoms was linked onto the magnetic core–shell structure. Then, Ni(II) ions were coordinated on the surface of the silica-coated MNPs and reduced to Ni(0) NPs to obtain the final catalyst. The catalytic activity of the prepared catalyst was studied for the synthesis of biaryl derivatives via the Suzuki–Miyaura cross-coupling reaction in high yields. The catalyst could also be recovered and reused with no loss of activity over five successful runs.
- Keyhaniyan, Mahdi,Khojastehnezhad, Amir,Eshghi, Hossein,Shiri, Ali
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- Silica-coated magnetic nanoparticles functionalized cobalt complex: a recyclable and efficient catalyst for the C?C bond formation
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In this study, the Co-based catalyst was prepared by cobalt immobilization on the surface of functionalized silica-coated magnetic NPs (Fe3O4@SiO2-CT-Co) as a magnetically core–shell nanocatalyst and characterized by FT-IR, TGA, XRD, VSM, SEM, TEM, EDX, EDX mapping, and ICP techniques and appraised in the Suzuki–Miyaura cross-coupling reaction under mild reaction conditions. The results displayed the superparamagnetic behavior of the Fe3O4 NPs core encapsulated by SiO2 shell, and the size of the particles was estimated about 30?nm. Compared with the previously reported catalysts, the engineered Fe3O4@SiO2-CT-Co catalyst provided perfect catalytic performance for the Suzuki–Miyaura cross-coupling reaction in water as a green solvent and it was much cheaper in the comparison with the traditional Pd-based catalysts. Importantly, the durability of magnetic nanocatalyst was studied and observed that it is stable under the reaction conditions and could be easily reused for at least six successive cycles without any significant decrease in its catalytic activity. Graphic abstract: [Figure not available: see fulltext.]
- Haqjow, Hanif,Raoufi, Farveh
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p. 4113 - 4128
(2021/07/26)
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- Discovery of Biphenyl-Sulfonamides as Novel β- N-Acetyl- d -Hexosaminidase Inhibitors via Structure-Based Virtual Screening
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Novel insecticidal targets are always in demand due to the development of resistance. OfHex1, a β-N-acetyl-d-hexosaminidase identified in Ostrinia furnacalis (Asian corn borer), is involved in insect chitin catabolism and has proven an ideal target for insecticide development. In this study, structure-based virtual screening, structure simplification, and biological evaluation are used to show that compounds with a biphenyl-sulfonamide skeleton have great potential as OfHex1 inhibitors. Specifically, compounds 10k, 10u, and 10v have Ki values of 4.30, 3.72, and 4.56 μM, respectively, and thus, they are more potent than some reported nonglycosyl-based inhibitors such as phlegmacin B1 (Ki = 26 μM), berberine (Ki = 12 μM), 2 (Ki = 11.2 μM), and 3 (Ki = 28.9 μM). Furthermore, inhibitory kinetic assessments reveal that the target compounds are competitive inhibitors with respect substrate, and based on toxicity predictions, most of them have potent drug properties. The obtained results indicate that the biphenyl-sulfonamide skeleton characterized by simple chemical structure, synthetic tractability, potent activity, and low toxicity has potential for further development in pest management targeting OfHex1.
- Chen, Tao,Li, Wen-Qin,Liu, Zheng,Jiang, Wen,Liu, Tian,Yang, Qing,Zhu, Xiao-Lei,Yang, Guang-Fu
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p. 12039 - 12047
(2021/10/20)
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- Preparation of metal-immobilized methacrylate-based monolithic columns for flow-through cross-coupling reactions
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With the aim of developing efficient flow-through microreactors for high-throughput organic synthesis, in this work, microreactors were fabricated by chemically immobilizing palladium-, nickel-, iron-, and copper-based catalysts onto ligand-modified poly(glycidyl methacrylate-co-ethylene dimethacrylate) [poly(GMA-co-EDMA)] monoliths, which were prepared inside a silicosteel tubing (10 cm long with an inner diameter of 1.0 mm) and modified with several ligands including 5-amino-1,10-phenanthroline (APHEN), iminodiacetic acid (IDA), and iminodimethyl phosphonic acid (IDP). The performance of the resulting microreactors in Suzuki?Miyaura cross-coupling reactions was evaluated, finding that the poly(GMA-co-EDMA) monolith chemically modified with 5-amino-1,10-phenanthroline as a binding site for the palladium catalyst provided an excellent flow-through performance, enabling highly efficient and rapid reactions with high product yields. Moreover, this monolithic microreactor maintained its good activity and efficiency during prolonged use.
- Sabarudin, Akhmad,Shu, Shin,Yamamoto, Kazuhiro,Umemura, Tomonari
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- Rigid chelating dicarbene ligands based on naphthyridine-fused bisimidazolium salts
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Naphthyridine-fused bisimidazolium salts were designed and synthesized for the first time. The study of the Cu(II) and Pd(II) complexes demonstrated that the deprotonated dicarbene ligands are rigid chelating C,C-ligands with strong electron-donating ability in analogy with the classic phenanthroline N,N-ligands.
- Gao, Ge,Liu, Yan,She, Zhijie,Wang, Tianbao,Zheng, Qinze,Zheng, Xuesong
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supporting information
(2021/11/26)
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- Micellar catalysis of the Suzuki Miyaura reaction using biogenic Pd nanoparticles fromDesulfovibrio alaskensis
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Microorganisms produce metal nanoparticles (MNPs) upon exposure to toxic metal ions. However, the catalytic activity of biosynthesised MNPs remains underexplored, despite the potential of these biological processes to be used for the sustainable recovery of critical metals, including palladium. Herein we report that biogenic palladium nanoparticles generated by the sulfate-reducing bacteriumDesulfovibrio alaskensisG20 catalyse the ligand-free Suzuki Miyaura reaction of abiotic substrates. The reaction is highly efficient (>99% yield, 0.5 mol% Pd), occurs under mild conditions (37 °C, aqueous media) and can be accelerated within biocompatible micelles at the cell membrane to yield products containing challenging biaryl bonds. This work highlights how native metabolic processes in anaerobic bacteria can be combined with green chemical technologies to produce highly efficient catalytic reactions for use in sustainable organic synthesis.
- Dennis, Jonathan A.,Era, Yuta,Horsfall, Louise E.,Wallace, Stephen
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supporting information
p. 8886 - 8890
(2021/11/23)
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- Magnetic chitosan-functionalized cobalt-NHC: Synthesis, characterization and catalytic activity toward Suzuki and Sonogashira cross-coupling reactions of aryl chlorides
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Aryl chlorides are one of the most stable and available electrophiles, however, their coupling with nucleophiles remains a challenge in organic synthesis. Herein, we prepared a Cobalt-NHC (N-Heterocyclic carbene) complex anchored on magnetic chitosan nanoparticles and assayed its catalytic activity for the reactions of substituted phenylboronic acid and also phenlacetylene with derivatives of aryl chlorides. These reactions are of great importance since they are employed for the synthesis of unsymmetrical diarylethynes and biphenyls, which belong to a prime class of building blocks. The synthesized nanocatalyst was found to be highly efficient in Suzuki and Sonogashira coupling in terms of their activity and recyclability in polyethylene glycol (PEG) as a green reaction media under conditions of temperatures (70 and 100 °C) and Co loading (3 and 6 mol%). To the best of our knowledge, this is the first attempt of using cobalt-NHC complex for catalyzing the abovementioned reactions. Moreover, replacing the earth-abundant Cobalt-based catalyst as an alternative to high cost palladium make this approach promising from sustainable chemistry view.
- Hajipour, Abdol R.,Malek, Shaghayegh Sadeghi
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- An unsymmetrical Schiff-base derived recyclable Pd-catalyst for Suzuki–Miyaura and Sonogashira reactions in aqueous media
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Abstract: A water-soluble palladium (II) complex containing an unsymmetrical Schiff-base ligand was synthesized and applied as catalyst Suzuki–Miyaura and Sonogashira cross-coupling reactions in aqueous media. Notably, moderate to excellent yields of biaryls were obtained in Suzuki reaction with usually less reactive aryl and heteroaryl chlorides under relatively mild condition. Moderate-to-high yields of aryl-alkynes were also obtained in Sonogashira reactions using aryl bromides. Apart from hydrophilic nature, the accomplishment of reactions in water, high recyclability, broad functional group tolerance, etc., are other advantages of the system. Graphic abstract: [Figure not available: see fulltext.]
- Das, Pankaj,Gogoi, Achinta,Puzari, Amlan
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- N-Heterocyclic Carbene–Palladium Complex onto Graphene Oxide and Poly (ethylene glycol) (PEG) Applied as Superior Catalyst for the Suzuki-Miyaura Cross-Coupling Reaction in Water
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Using polymeric nanocomposites incorporated Pd to promote C-C coupling reactions has been found as one of the most successful strategies. In this paper we apply graphene oxide (GO) as an efficient surface immobilized by water-soluble poly (ethylene glycol)-imidazole followed by introduction of PdCl2 salt to obtain the desired catalyst. Catalytic performance of this composite was investigated in the Suzuki–Miyaura cross-coupling reaction under mild reaction conditions and superior results were obtained. The hydrophilic nature of the catalyst and well distribution of Pd lead to superior catalytic activity in water media. Moreover, the Suzuki–Miyaura reaction proceed successfully with excellent yield and short reaction time without any loss of activity even after seven consecutive reaction cycles.
- Heravi, Majid M.,Asadi, Shima,Hoseini Chopani, Seyede Mahdiye,Jaderi, Elham
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- Palladium (II)–Salan Complexes as Catalysts for Suzuki–Miyaura C–C Cross-Coupling in Water and Air. Effect of the Various Bridging Units within the Diamine Moieties on the Catalytic Performance
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Water-soluble salan ligands were synthesized by hydrogenation and subsequent sulfonation of salens (N,N’-bis(slicylidene)ethylenediamine and analogues) with various bridging units (linkers) connecting the nitrogen atoms. Pd (II) complexes were obtained in reactions of sulfosalans and [PdCl4]2?. Characterization of the ligands and complexes included extensive X-ray diffraction studies, too. The Pd (II) complexes proved highly active catalysts of the Suzuki–Miyaura reaction of aryl halides and arylboronic acid derivatives at 80 ?C in water and air. A comparative study of the Pd (II)–sulfosalan catalysts showed that the catalytic activity largely increased with increasing linker length and with increasing steric congestion around the N donor atoms of the ligands; the highest specific activity was 40,000 (mol substrate) (mol catalyst × h)?1. The substrate scope was explored with the use of the two most active catalysts, containing 1,4-butylene and 1,2-diphenylethylene linkers, respectively.
- Bunda, Szilvia,Joó, Ferenc,Kathó, ágnes,Udvardy, Antal,Voronova, Krisztina
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supporting information
(2020/09/18)
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- Aqueous Suzuki-Miyaura coupling with ultralow palladium loading and simple product separation
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The diphosphine ligand N, N -bis(diphenylphosphanylmethyl)-aniline (bdppma) and PdCl 2afforded a Suzuki-Miyaura catalyst [(bdppm-)PdCl 2] that was highly efficient at an ultralow catalyst loading (0.001 mol%) in 20:1 H 2O-EtOH. This low catalyst loading in an aqueous solvent system permitted simple product separation by direct filtration without the need for chromatography. The ligand bdppma imparted surprisingly better reactivity than that achieved with other bidentate diphosphine ligands, but the catalytic system had a slightly narrower substrate scope than some similar Pd catalysts reported previously.
- Yang, Wei,Xu, Wen-Di,Ning, Jin-Jiao,Ren, Zhi-Gang,Young, David James
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supporting information
p. 1303 - 1307
(2020/08/21)
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- Antioxidant properties of synthesis nanometallic Pd-Ni?2-mercaptoethanol as effective catalyst for suzuki-miyaura reactions
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The palladium-catalyzed Suzuki coupling reaction is one of the most efficient strategies for constructing a carbon-carbon bond. In recent years, bimetallic catalysts have become candidates for the Suzuki coupling reaction. In this work, Pd-Ni?2-Mercaptoethanol nanoparticles were synthesized for the Suzuki-Miyaura cross-coupling of arylboronic acids with aryl bromides, in the N,N-dimethylformamide/water mixture catalyzed by Pd-Ni: A simple and efficient reaction performed in a solvent, without a ligand, and in open air. We found that the Suzuki-Miyaura reactions are remarkably fast (5 min), with high yields and the products are highly pure. The Pd-Ni?2-Mercaptoetanol nanoparticles have a narrow size distribution with a mean crystallite size of 10 nm. Radical scavenging activities of the complexes have been evaluated by using DPPH, DMPD+ and ABTS+ assays. IC50 values (μg/ml) of the complexes and standards on DPPH, DMPD+ and ABTS+ respectively following the sequences.
- Said, Khemais,Mesni, Ali,Salem, Ridha B.
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- A photocatalytic ensemble HP-T?Au-Fe3O4: Synergistic and balanced operation in Kumada and Heck coupling reactions
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A supramolecular catalytic ensemble HP-T?Au-Fe3O4 supported by highly branched assemblies of hexaphenylbenzene (HPB) derivatives has been developed. The as-prepared HP-T?Au-Fe3O4 nanohybrid material serves as an efficient catalytic system to prepare biaryl derivatives through the Kumada cross-coupling reaction using aryl chlorides as one of the coupling partners under mild reaction conditions (visible light irradiation, aqueous media, aerial conditions, short reaction time). Through the cooperative effect of Au NPs and Fe3O4 NPs, dual activation of aryl chlorides for the generation of aryl radical intermediates is achieved. On the other hand, oligomeric assemblies contributed significantly to the enhancement of the reaction rate and yield of the product by facilitating the reductive elimination step. Different mechanistic studies confirm the involvement of Au NPs, Fe3O4 NPs and oligomeric assemblies in the synergistic and balanced operation of HP-T?Au-Fe3O4 nanohybrid materials in the efficient completion of the catalytic cycle of the Kumada coupling reaction. Being magnetic, the catalytic ensemble could be recycled for up to five catalytic cycles. The as-prepared supramolecular photocatalytic ensemble also works efficiently in Heck coupling reactions involving aryl chlorides and aryl iodides as the coupling partner.
- Bhalla, Vandana,Kaur, Harpreet,Kumar, Manoj
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supporting information
p. 8036 - 8045
(2020/11/30)
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- Copper catalysed Gomberg-Bachmann-Hey reactions of arenediazonium tetrafluoroborates and heteroarenediazonium o-benzenedisulfonimides. Synthetic and mechanistic aspects
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Gomberg-Bachmann-Hey reactions were carried out in the presence of copper as a catalyst and gave rise to biaryls or heterobiaryls in good yields and in mild reaction conditions. A computational study of some key points of the reaction was performed. The results are coherent with the experimental data and confirm some aspects of the mechanism. The reaction free energies for the reduction in benzene by CuI of a set of 40 (hetero)arenediazonium tetrafluoroborates were calculated. Both the experiments and the calculations showed that in the coupling with substituted solvents (toluene, bromobenzene, nitrobenzene and anisole) the binding to the ortho position was always favoured.
- Antenucci, Achille,Barbero, Margherita,Dughera, Stefano,Ghigo, Giovanni
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- Exhaustive Reduction of Esters Enabled by Nickel Catalysis
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We report a one-step procedure to directly reduce unactivated aryl esters into their corresponding tolyl derivatives. This is achieved by an organosilane-mediated ester hydrosilylation reaction and subsequent Ni/NHC-catalyzed hydrogenolysis. The resulting conditions provide a direct and efficient alternative to multi-step procedures for this transformation that often require the use of hazardous metal hydrides. Applications in the synthesis of -CD3-containing products, derivatization of bioactive molecules, and chemoselective reduction in the presence of other C-O bonds are demonstrated.
- Cook, Adam,Prakash, Sekar,Zheng, Yan-Long,Newman, Stephen G.
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supporting information
p. 8109 - 8115
(2020/05/20)
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- "water soluble" palladium nanoparticle engineering for C-C coupling, reduction and cyclization catalysis
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The use of Pd nanoparticles (Pd-NPs) to realize several important organic reactions allows efficient catalysis with low metal loading (1000 ppm), hence providing a greener catalytic system. However, to be truly green Pd-NPs need to be synthesized in a sustainable manner and be able to react in aqueous media in order to avoid the use of organic solvents. Here we describe an original and eco-friendly synthesis of Pd-NPs (using benign reactants and simple conditions) perfectly stable in water. Remarkably, this synthesis allows for control over their size and morphology by simply tuning the pH of the stabilizer. We then evaluate the catalytic efficiency of these Pd-NPs on six different model reactions (Suzuki Miyaura, Sonogashira, Heck, nitrophenol reduction and pentynoic cycloisomerization) in aqueous media. We show that the stabilizer structure influences the activity owing to its ability to promote the mass transfer of the organic substrates towards the NP surface in the aqueous environment. Finally, catalytic evaluations show that our nano-catalysts prepared in an eco-friendly manner are among the best catalysts described so far in the literature in each case, with high turnover frequencies reached with a low loading of palladium.
- Iben Ayad,Belda Marín,Colaco,Lefevre,Méthivier,Ould Driss,Landoulsi,Guénin
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supporting information
p. 6646 - 6657
(2019/12/26)
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- Salicylaldehyde-stabilized palladium nanoparticles for highly efficient suzuki-miyaura reaction at room temperature
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Pd-catalyzed Suzuki-Miyaura cross-coupling reactions promoted by simple and commercial salicylaldehyde-based ligands were investigated. The effect of the ligands was evaluated and the reaction conditions were optimized. Moreover, the physical nature of the palladium was determined by TEM analysis and poison tests. It demonstrated that this catalytic system can be reused for ten consecutive runs and showed excellent activities toward aryl bromides with arylboronic acids at room temperature in air.
- Zhou, Zhen,Cao, Gao,Liu, Ning
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supporting information
p. 547 - 550
(2019/06/11)
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- Synthesis, characterization and catalytic performance of palladium supported on pyridine-based covalent organic polymer for Suzuki-Miyaura reaction
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A bipyridine-based covalent organic polymer (COP) was successfully synthesized by condensation of trimesoyl chloride (TMC) and 2,2′-bipyridine-5,5′-diamine (Bpy) under ambient conditions. This material was modified by coordination of PdCl2 to COP framework, affording a hybrid material, Pd@TMC-Bpy COP, which was applied as a highly efficient heterogeneous catalyst for Suzuki-Miyaura reaction under ligand-free conditions in ethyl lactate. The catalyst could be reused for five times without obvious loss of its activity.
- Han, Yi,Di, Jia-Qi,Zhao, Ai-Dong,Zhang, Zhan-Hui
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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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- Development of dipyridine-based coordinative polymers for reusable heterogeneous catalysts
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Poly(di(pyridin-2-yl)methyl acrylate) (PDPyMA), which was obtained by the free radical polymerization of designed coordinative monomer of di(pyridin-2-yl)methyl acrylate, is able to coordinate with various metal ions to form heterogeneous catalysts for diverse catalytic reactions. The Pd and Cu complexes supported by PDPyMA were developed for the heterogeneous Suzuki-Miyaura reaction and Friedel-Crafts alkylation, respectively. The PDPyMA-based catalysts showed no significant decline of reactivity after five times recycling. However, the hydrolysis of the PDPyMA backbone under alkaline conditions limited the catalytic efficiency of this heterogeneous catalyst so that the coordinative monomer was redesigned as 1,1-di(pyridine-2-yl)-2-(4-vinylphenyl)ethan-1-ol and then 2,2′-(1-methoxy-2-(4-vinylphenyl)ethane-1,1-diyl)dipyridine (MVPhDPy). With copolymerization of N-isopropyl acrylamide (NIPAM), the efficiency of polymer-based heterogeneous catalysts could be further raised, demonstrated by the increased turn over number in the Suzuki-Miyaura reaction, which approached 5,260 by using the catalyst formed from poly(MVPhDPy-co-NIPAM) and Pd(OAc)2. poly(MVPhDPy-co-NIPAM) copolymer, therefore, could be a versatile platform to support different metal ions for various heterogeneous catalytic reactions.
- Chang, Hsiang-Chun,Li, Jia-Qi,Lin, Ching-Kai,Hsu, Yu-Jung,Tu, Tsung-Han,Hsieh, Yi-Liang,Hsu, Hsiu-Hao,Lee, Gene-Hsiang,Liu, Yi-Hung,Peng, Chi-How
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p. 1119 - 1133
(2019/08/01)
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- An N-heterocyclic carbene-functionalised covalent organic framework with atomically dispersed palladium for coupling reactions under mild conditions
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Covalent organic frameworks (COFs) are a new class of crystalline porous materials that could function as excellent scaffolds for heterogeneous catalysts. Herein, we report a functionalised COF (COF-NHC) using N-heterocyclic carbene (NHC) as a monomer building block via a facile ionothermal strategy. The simple and easily prepared imine-linked COF-NHC possessed two coordination sites (NHC and amine), which could fix the active component (Pd) tightly in COF, leading to atomically dispersed Pd in a heterogeneous catalyst. The as-prepared Pd@COF-NHC showed high stability in the Suzuki-Miyaura coupling reaction of arylboronic acids and aryl halides in aqueous media at room temperature, and could be easily recycled and reused multiple times without the loss of catalytic activity. Moreover, C-C coupling reactions could be accomplished using triarylbismuth reagents in ethanol aqueous solutions with high yields.
- Yang, Junjuan,Wu, Yuanyuan,Wu, Xiaowei,Liu, Wenjing,Wang, Yaofang,Wang, Junwen
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supporting information
p. 5267 - 5273
(2019/10/11)
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- Thiazole-based non-symmetric NNC-palladium pincer complexes as catalytic precursors for the Suzuki-Miyaura C-C coupling
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We report an efficient synthesis of new non-symmetric pincer palladacycles 2a-i, containing a [NNC]-tridentate ligand formed by a hydrazone and a thiazolyl moiety as sources of N-donor atoms. These catalytic precursors were tested in the Suzuki-Miyaura cross coupling reaction using a variety of aryl boronic acids with aryl bromides or chlorides using water as solvent. Complex 2a displays the best catalytic performance under aerobic conditions, affording the coupling products in good to high yields. In all cases, the cross-coupling reaction was conducted under IR irradiation, allowing a decrease in the reaction time.
- Camacho-Espinoza, Martín,Reyes-Deloso, Alberto,Toscano, R. Alfredo,Penieres-Carrillo, J. Guillermo,López-Cortés, José G.,Ortega-Alfaro, M. Carmen,Ortega-Jiménez, Fernando
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p. 12967 - 12978
(2019/08/30)
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- Atom-efficient Pd-catalyzed cross-couplings of chloroarenes with triarylbismuth reagents
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Various Pd-catalyzed protocols have been developed for the atom-efficient cross-coupling of chloroarenes with triarylbismuth reagents. Using the developed protocols, an efficient synthesis of unsymmetrical biaryls in good to excellent yields was achieved by employing electron-deficient chloroarenes and a range of triarylbismuth reagents.
- Rao, Maddali L.N.,Meka, Suresh
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supporting information
(2019/07/30)
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- Anthranilamide (aam)-substituted arylboranes in direct carbon-carbon bond-forming reactions
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Anthranilamide (aam)-substituted arylboranes, which were reported to serve as masked boranes in the Suzuki-Miyaura coupling, have been found to be directly cross-coupled just by use of an aqueous medium. The excellent stability of 2-pyridyl-B(aam) toward protodeborylation allowed their smooth cross-coupling.
- Kamio, Shintaro,Kageyuki, Ikuo,Osaka, Itaru,Yoshida, Hiroto
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supporting information
p. 2624 - 2627
(2019/03/05)
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- Assembly immobilized palladium(0) on carboxymethylcellulose/Fe3O4 hybrid: An efficient tailor-made magnetically catalyst for the Suzuki–Miyaura couplings
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The Pd nanoparticles (Pd NPs) embedded on magnetically retrievable carboxymethylcellulose/Fe3O4 (Pd0@CMC/Fe3O4) organic/inorganic hybrid were prepared via the conventional simple process. The presence of the hydroxyl and carboxyl groups within the framework of the magnetic hybrid enables the facile preparation and stabilization of Pd NPs in this organic/inorganic hybrid. This hybrid catalyst was very effective in the Suzuki–Miyaura reaction of a variety of aryl halides with arylboronic acid to afford excellent product yields. The catalyst showed good stability and could be easily recovered with an external magnetic field and reused for several times without a significant loss in its catalytic activity. Furthermore, the Pd0@CMC/Fe3O4 hybrid catalyst was fully characterized by UV–Vis, FT–IR, XRD, SEM, EDX, TEM, XPS and TGA techniques. The hot filtration test suggests that a homogeneous mechanism is operative in Suzuki–Miyaura reaction.
- Zhang, Zhuan,Zhang, Yizong,Liu, Xiaoping,Shen, Binbin,Zhang, Tianzhu,Li, Yiqun
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- Organic Solvent-Free, Pd(II)-Salan Complex-Catalyzed Synthesis of Biaryls via Suzuki-Miyaura Cross-Coupling in Water and Air
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With use of a Pd(II)-sulfosalan complex as a water-soluble catalyst, we have developed an efficient synthesis of biaryls via Suzuki-Miyaura cross-coupling in water under aerobic conditions. The water-insoluble target molecules were isolated by simple filtration in analytical purity after washing with 0.01 M aqueous HCl (20 examples). In most cases, palladium contamination was below 5 ppm considered acceptable for active pharmaceutical ingredients. The established method is scalable, reproducible, and provides biaryl products in isolated yields up to 91%.
- Bunda, Szilvia,Udvardy, Antal,Voronova, Krisztina,Joó, Ferenc
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p. 15486 - 15492
(2019/01/03)
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- A highly recoverable polymer-supported ionic salen-palladium complex as a catalyst for the Suzuki-Miyaura cross coupling in neat water
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A polymer supported Pd-salen complex (PS-Pd-salen) was synthesized and characterized by Fourier transform infrared spectroscopy (FT-IR), Fourier-transform NMR spectroscopy (FT-NMR), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), surface area and pore size distribution by Brunauer-Emmett-Teller (BET). The heterogeneous catalytic performance of the PS-Pd-salen for the Suzuki-Miyaura coupling of variety of phenyl boronic acid with different aryl halides was successfully conducted in water with K2CO3 and 20 mg catalyst loading at room temperature. The coupling reactions with aryl iodides and bromides were achieved at room temperature with good to excellent yield; whereas the reactions with aryl chlorides were performed in aqueous-ethanol (1:1) at 90 °C. The product yields related with the substrates were optimized, and main reaction factors influencing the yields were also recognized. The results clearly indicated that the reaction constraints needed to achieve high yields are substrate-reliant. The hot filtration test verified heterogeneous nature of PS-Pd-salen complex. Moreover, the catalyst showed excellent reusability for five successive runs in slight compromising with its activity.
- Balinge, Kamlesh Rudreshwar,Khiratkar, Avinash Ganesh,Bhagat, Pundlik Rambhau
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p. 131 - 139
(2017/12/07)
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- Palladium-Loaded Cucurbit[7]uril-Modified Iron Oxide Nanoparticles for C?C Cross-Coupling Reactions
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Cucurbit[7]uril modified iron oxide nanoparticles (CB[7]NPs) were loaded with palladium to form nano-catalysts (Pd@CB[7]NPs) that, with microwave heating, catalysed Suzuki–Miyaura, Sonogashira, and Mizoroki–Heck cross-coupling reactions. Reactions were run in environmentally benign 1:1 ethanol/water solvent under convenient aerobic conditions. In a preliminary screening, conversions and yields were uniformly high with turn over frequencies (TOF) ranging from 64 to 7360 h?1. The nano-catalysts could be recovered with a magnet and reused several times (6 times for Suzuki–Miayura reaction) without loss of activity.
- Benyettou, Farah,Motte, Laurence,Traboulsi, Hassan,Mazher, Javed,Pasricha, Renu,Olsen, John-Carl,Trabolsi, Ali,Guenin, Erwan
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supporting information
p. 2349 - 2353
(2018/02/06)
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- Rapid “Mix-and-Stir” Preparation of Well-Defined Palladium on Carbon Catalysts for Efficient Practical Use
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A facile direct deposition approach for the preparation of recyclable Pd/C catalysts simply by stirring a solution of tris(dibenzylideneacetone)dipalladium(0) with a suitable carbon material was evaluated. An extraordinarily rapid catalyst preparation procedure (0 centers onto the highly accessible surface area and the avoidance of ill-defined PdII/Pd0 states.
- Yakukhnov, Sergey A.,Pentsak, Evgeniy O.,Galkin, Konstantin I.,Mironenko, Roman M.,Drozdov, Vladimir A.,Likholobov, Vladimir A.,Ananikov, Valentine P.
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p. 1869 - 1873
(2018/04/30)
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- Pd/REOs catalysts applied to the Suzuki-Miyaura coupling. A comparison of their catalytic performance and reusability
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Two new palladium catalysts based on rare earth oxide supports, namely, Pd/Dy2O3 and Pd/Yb2O3 were prepared by the incipient wetness impregnation method, followed by calcination at 600 °C. Both compounds, which were fully characterized, were tested as catalysts in the Suzuki-Miyaura reaction and their catalytic activity was compared with that of already known Pd/La2O3, Pd/CeO2, Pd/Pr6O11, Pd/Sm2O3, and Pd/Gd2O3. It has been found that the nature of the support strongly affects the catalytic activity. The scope of the catalytic protocol was investigated and quantitative yields of the coupling products (21 examples are reported) were always observed using a low metal amount (0.05 mol%). A systematic investigation on the reusability of the entire set of catalytic systems has been carried out. All catalysts showed to be successfully recyclable, and also in this case the nature of the rare earth element is crucial. The highest reusability was observed for catalysts Pd/CeO2 and Pd/Sm2O3.
- Del Zotto, Alessandro,Colussi, Sara,Trovarelli, Alessandro
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p. 275 - 283
(2017/09/30)
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- Novel ferrocenebidentate ligand and method for preparing catalyst through coordination of ligand and copper salt
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The invention discloses a novel ferrocenebidentate ligand and a method for preparing a catalyst through coordination of the ligand and copper salt. The novel ferrocenebidentate ligand is taken as theligand for coordination with different types of copper salt, a Suzuki-Miyaura reaction is catalyzed, and the relatively high yield is obtained under mild conditions. The catalyst has the characteristics of being simple in preparation, convenient in operation and high in reaction yield and being beneficial for large-scale application.
- -
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Paragraph 0015
(2019/01/08)
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- Picolinamide modified β-cyclodextrin/Pd (II) complex: Asupramolecular catalyst for Suzuki-Miyaura coupling of aryl, benzyl and allyl halides with arylboronic acids in water
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Novel supramolecular catalysts for Suzuki-Miyaura coupling were prepared and characterized by NMR, FT-IR, TEM, XRD, TGA, and XPS. The resulting picolinamide-modified β-cyclodextrin/Pd(II) complex (Pd(II)@PCA-β-CD) showed very efficient catalytic activity for Suzuki-Miyaura coupling of aryl, benzyl, and allyl halides with arylboronic acids in an environmentally benign aqueous solution. Various organic halides including chlorides can produce good to excellent yields with phenyl-boronic acid and a catalytic amount of Pd(II)@PCA-β-CD. This hydro-soluble catalyst was capable of being reused for at least eight runs with only a slight loss of catalytic activity. A putative mechanism of the Pd(II)/Pd(IV) catalytic cycle was also explored and calculated by ab initio QM/MM methods.
- Luo, Kaixiu,Zhang, Lu,Yang, Rui,Jin, Yi,Lin, Jun
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p. 200 - 210
(2018/08/09)
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- Thioether–NHC-Ligated PdII Complex for Crafting a Filtration-Free Magnetically Retrievable Catalyst for Suzuki–Miyaura Coupling in Water
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A new benzimidazolium salt, 1-[benzylaminocarbonylmethyl]-3-(2-phenylsulfanylethyl)-1H-benzimidazolium chloride (L), which is a precursor of a novel thioether-functionalized NHC, has been synthesized by subjecting 1H-benzimidazole to a sequence of reactions with 1,2-dichloroethane, sodium thiophenolate, and N-benzyl-2-chloroacetamide, successively. The moisture/air-insensitive complex [Pd(L–HCl)Cl2] (1) was prepared by the reaction of L with PdCl2. The molecular structure of 1, established by X-ray crystallography, revealed a square-planar geometry around Pd. Complex 1 was screened for Suzuki–Miyaura coupling reactions of various aryl/heteroaryl bromides (yields of up to 94 % in 2 h) in water at room temperature. Furthermore, complex 1 was immobilized onto the surface of aminopropyl-functionalized silica-coated magnetite nanoparticles [NPs, Fe3O4@SiO2-(CH2)3-NH2] by a stepwise modification strategy to develop the heterogeneous magnetically retrievable catalyst Fe3O4@SiO2-1′, in which the amide functionality present in the side-arm of the NHC within the NHC–PdII complex serves as linker. This magnetic nanosupport, bearing palladium complexes incorporating a novel thioether-based NHC ligand that functions in aqueous aerobic medium and can be easily separated, renders Fe3O4@SiO2-1′ a most desirable catalyst for the Suzuki–Miyaura coupling reaction. It was also observed that the catalyst was effective for up to seven cycles and was easily separated from the reaction medium by the use of an external magnet, further increasing its appeal.
- Nayan Sharma, Kamal,Satrawala, Naveen,Kumar Joshi, Raj
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p. 1743 - 1751
(2018/05/14)
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- One-Pot Tandem Photoredox and Cross-Coupling Catalysis with a Single Palladium Carbodicarbene Complex
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The combination of conventional transition-metal-catalyzed coupling (2 e? process) and photoredox catalysis (1 e? process) has emerged as a powerful approach to catalyze difficult cross-coupling reactions under mild reaction conditions. Reported is a palladium carbodicarbene (CDC) complex that mediates both a Suzuki–Miyaura coupling and photoredox catalysis for C?N bond formation upon visible-light irradiation. These two catalytic pathways can be combined to promote both conventional transition-metal-catalyzed coupling and photoredox catalysis to mediate C?H arylation under ambient conditions with a single catalyst in an efficient one-pot process.
- Hsu, Yu-Cheng,Wang, Vincent C.-C.,Au-Yeung, Ka-Chun,Tsai, Chung-Yu,Chang, Chun-Chi,Lin, Bo-Chao,Chan, Yi-Tsu,Hsu, Chao-Ping,Yap, Glenn P. A.,Jurca, Titel,Ong, Tiow-Gan
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supporting information
p. 4622 - 4626
(2018/03/21)
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- The β-cyclodextrin decorated with palladium nanoparticles without pretreatment: An efficient heterogeneous catalyst for biaryls synthesis
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β-Cyclodextrin decorated with palladium nanoparticles (PdNPs@β-CD) without pretreatment led to a suitable catalyst for the biaryls synthesis in water. A simple and straightforward method was developed for the preparation of PdNPs@β-CD as a green catalyst. The prepared catalyst was characterized by Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), atomic absorption spectroscopy (AAS), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDS) measurements. It was found that PdNPs@β-CD exhibits high performance in Ullmann, Suzuki and Hiyama coupling reactions.
- Feiz, Afsaneh,Loni, Masood,Naderi, Soheila,Bazgir, Ayoob
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- Magnetically recyclable Pd/Fe3O4/g-C3N4 as efficient catalyst for the reduction of nitrophenol and suzuki-miyaura reaction at room temperature
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Herein, we present the design and synthesis of a novel magnetic stable and recyclable catalyst Pd/Fe3O4/g-C3N4 with approachable active palladium nanoparticles (Pd NPs) based on the platelet-like graphitic carbon nitrides (g-C3N4). The Pd NPs, g-C3N4 and magnetic particles (Fe3O4) are tightly connected through non-covalent interactions owing to the layered structure of g-C3N4 with abundant nitrogen atoms, facilitating the stability of Pd/Fe3O4/g-C3N4 and activating the Pd NPs at the same time. The Pd/Fe3O4/g-C3N4 catalyst with a narrow particle size distribution (2.55 nm) of Pd NPs displayed the maintenance of the planar structure of g-C3N4. The activity parameter of the catalyst turned out to be excellent (12.4 s11¢mM11) by fitting the curves derived from the reduction of nitrophenol. Meanwhile, the Suzuki-Miyaura coupling reaction at room temperature processed smoothly with the Pd/Fe3O4/g-C3N4 catalyst. It is meaningful to stress that 2-bromobenzonitrile and p-tolylboronic acid could afford the medical intermediate sartanbiphenyl at total conversion without side reactions in 25 min. Furthermore, the nanocatalyst owes the properties of easy recycling using a powerful magnet as well as high turnover frequency (at least 5 runs) with retention of high catalytic activity.
- Yang, Yingwei,Tang, Ruiren
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p. 544 - 547
(2018/04/09)
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- Palladium complexes with two unsymmetrical Schiff base ligands: Highly active catalyst for activation of chloroarenes in Suzuki-Miyaura reaction
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Two new unsymmetrical Schiff base derived palladium(II) complexes, [PdCl2{bis(salicylidene)-2-aminobenzamide}] (C1) and [PdCl2{N,N'-bis(salicylidene)-2-aminobenzylamine}] (C2) have been synthesized and characterized. The complexes have been explored as catalysts for the Suzuki-Miyaura cross-coupling reactions of aryl halides with arylboronic acids. An optimization study reveals that under similar experimental conditions, the complex C1 shows superior activity over the complex C2. Using the complex C1 as catalyst, less reactive chloroarenes are efficiently converted to their corresponding biaryls under relatively mild conditions (80oC, 0.5 mol% catalyst) using EtOH as an environmentally safer reaction media. Excellent yields of cross coupling products are also obtained with aryl bromides at room temperature in neat water with low catalyst loading (0.02 mol %).
- Puzari, Amlan,Shahnaz, Nasifa,Das, Pankaj
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p. 837 - 842
(2020/06/26)
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- Integrating Organic Lewis Acid and Redox Catalysis: The Phenalenyl Cation in Dual Role
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In recent years, merging different types of catalysis in a single pot has drawn considerable attention and these catalytic processes have mainly relied upon metals. However, development of a completely metal free approach integrating organic redox and organic Lewis acidic property into a single system has been missing in the current literature. This study establishes that a redox active phenalenyl cation can activate one of the substrates by single electron transfer process while the same can activate the other substrate by a donor-acceptor type interaction using its Lewis acidity. This approach has successfully achieved light and metal-free catalytic C-H functionalization of unactivated arenes at ambient temperature (39 entries, including core moiety of a top-selling molecule boscalid), an economically attractive alternative to the rare metal-based multicatalysts process. A tandem approach involving trapping of reaction intermediates, spectroscopy along with density functional theory calculations unravels the dual role of phenalenyl cation.
- Ahmed, Jasimuddin,Chakraborty, Soumi,Jose, Anex,Sreejyothi,Mandal, Swadhin K.
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supporting information
p. 8330 - 8339
(2018/06/19)
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- Cyrene as a Bio-Based Solvent for the Suzuki-Miyaura Cross-Coupling
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The Suzuki-Miyaura (SM) cross-coupling is the most broadly utilized Pd-catalyzed C-C bond-forming reaction in the chemical industry. A large proportion of SM couplings employ dipolar aprotic solvents; however, current sustainability initiatives and increasingly stringent regulations advocate the use of alternatives that exhibit more desirable properties. Here we describe the scope and utility of the bio-derived solvent Cyrene in SM cross-couplings and evaluate its suitability as a reaction medium for this benchmark transformation from discovery to gram scale.
- Wilson, Kirsty L.,Murray, Jane,Jamieson, Craig,Watson, Allan J. B.
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supporting information
p. 650 - 654
(2017/12/26)
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- Stannylation of Aryl Halides, Stille Cross-Coupling, and One-Pot, Two-Step Stannylation/Stille Cross-Coupling Reactions under Solvent-Free Conditions
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Solvent-free protocols for palladium-catalyzed stannylation of aryl halides, Stille cross-coupling, and one-pot, two-step stannylation/Stille cross-coupling (SSC) are reported for the first time. (Het)aryl halides bearing acceptor, donor, as well as sterically demanding substituents are stannylated and/or coupled in high yields. The reactions are catalyzed by conventional palladium(II) acetate/PCy3 [Pd(OAc)2/PCy3] under air, using available base CsF, and without the use of high purity reagents. The developed synthetic procedures are versatile, robust, and easily scalable. The absence of solvent, and the elimination of isolation procedures of aryl stannanes makes the SSC protocol simple, step economical, and highly efficient for the synthesis of biaryls in a one-pot two-step procedure.
- Gribanov, Pavel S.,Golenko, Yulia D.,Topchiy, Maxim A.,Minaeva, Lidiya I.,Asachenko, Andrey F.,Nechaev, Mikhail S.
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p. 120 - 125
(2018/01/17)
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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 0040; 0041; 0042; 0044
(2018/09/21)
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