- 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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- Highly Active Fe3O4@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction
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A novel Pd-NHC functionalized magnetic Fe3O4@SBA-15@NHC-Pd was synthesized and used as an efficient heterogeneous catalyst in the Suzuki–Miyaura C–C bond formation reactions. The Fe3O4@SBA-15@NHC-Pd characterized by X-Ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy?(TEM), Energy Dispersive X-ray analysis (EDX), Thermogravimetric Analysis (TGA), Differential Thermal Analysis (DTA). The Inductively Coupled Plasma-Optical emission spectroscopy (ICP-OES)?analysis was used to determine the exact amount of Pd (0.33?wt%) in Fe3O4@SBA-15@NHC-Pd. The TEM images of the catalyst showed the existence of palladium nanoparticles immobilized in the catalyst's structure, while no reducing agent was used. The NHC moieties in the catalyst structure could be stabilize Pd(0) nanoparticles prevents agglomeration. The magnetic catalyst was effectively used in the Suzuki–Miyaura cross-coupling reaction of substituted phenylboronic acid derivatives with (hetero)aryl bromides in the presence of a K2CO3 at room temperature in aqueous media and magnetic catalyst could be simply extracted from the reaction mixture by an external magnet. Different aryl bromides were converted to coupled-products in excellent yields with spectacular TOFs values (up to 1,960,339?h?1); in the presence of 1?mg of Fe3O4@SBA-15@NHC-Pd catalyst (contains 3.1 × 10–6?mol% Pd) at room temperature in aqueous media. After reusability experiments, it is found that this catalyst was effectively used up to ten times in the reaction with almost consistent catalytic efficiency. A decrease in the activity of the 10th reused catalyst was found as 9%. Graphic Abstract: [Figure not available: see fulltext.]
- ?zdemir, ?smail,Akko?, Mitat,Alt?n, Serdar,Bu?day, Nesrin,Ya?ar, Sedat
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- Magnetite@MCM-41 nanoparticles as support material for Pd-N-heterocyclic carbene complex: A magnetically separable catalyst for Suzuki–Miyaura reaction
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The Magnetite@MCM-41@NHC@Pd catalyst was obtained with Pd metal bound to the NHC ligand anchored to the surface of Fe3O4@MCM-41. It was characterized by Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy disperse X-ray analysis (EDX), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and scanning electron microscopy (SEM). The amount of Pd in the Magnetite@MCM-41@NHC@Pd was measure by inductively coupled plasma–optical emission spectroscopy (ICP-OES) analysis. The catalytic activity of Magnetite@MCM-41@NHC@Pd heterogeneous catalyst done on Suzuki–Miyaura reactions of aryl halides with different substituted arylboronic acid derivatives. All coupling reactions afforded excellent yields and up to 408404 Turnover Frequency (TOF) h?1 in the presence of 2 mg of Magnetite@MCM-41@NHC@Pd catalyst (0.0564 mmol g?1, 0.01127 mmol% Pd) at room temperature in 2-propanol/H2O (1:2). Moreover, Magnetite@MCM-41@NHC@Pd catalyst was recover by applying the magnet and reused for another reaction. The catalyst showed excellent structural and chemical stability and reused ten times without a substantial loss in its catalytic performance.
- Akko?, Mitat,Bu?day, Nesrin,Alt?n, Serdar,Ya?ar, Sedat
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- N-heterocyclic carbene Pd(II) complex supported on Fe3O4@SiO2: Highly active, reusable and magnetically separable catalyst for Suzuki-Miyaura cross-coupling reactions in aqueous media
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A new type magnetic nano Fe3O4@SiO2@NHC@Pd-MNPs heterogeneous catalyst was fabricated and characterized by Fourier Transform Infrared (FTIR) spectroscopy, Transmission Electron Microscopy (TEM), X-Ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Energy Disperse X-ray analysis (EDX), Thermogravimetric Analysis (TGA), Differential Thermal Analysis (DTA), and Scanning Electron Microscopy (SEM). The loading amount of Palladium (Pd) to magnetic nano Fe3O4@SiO2@NHC@Pd-MNPs was measured by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) analysis. The catalytic activity of magnetic nano Fe3O4@SiO2@NHC@Pd-MNPs heterogeneous catalyst was examined on Suzuki-Miyaura cross-coupling reactions of aryl halides with different substituted arylboronic acid derivatives. All coupling reactions yielded excellent results and high TOF (up to 76528 h?1) in the presence of 2 mg of Fe3O4@SiO2@NHC@Pd-MNPs catalyst (0.0197 mmolg?1, 0.00394 mmol%Pd) at 80 °C in 2-propanol/H2O (1:2). In addition, the magnetic nano Fe3O4@SiO2@NHC@Pd-MNPs catalyst was easily recovered by using an external Nd-magnet and reused for the Suzuki cross-coupling reactions. The catalyst showed strong structural and chemical stability and was reused six times without losing its catalytic activity substantially.
- Akko?, Mitat,Bu?day, Nesrin,Alt?n, Serdar,Kiraz, Nadir,Ya?ar, Sedat,?zdemir, ?smail
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- Decarbonylative Synthesis of Aryl Nitriles from Aromatic Esters and Organocyanides by a Nickel Catalyst
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A decarbonylative cyanation of aromatic esters with aminoacetonitriles in the presence of a nickel catalyst was developed. The key to this reaction was the use of a thiophene-based diphosphine ligand, dcypt, permitting the synthesis of aryl nitrile without the generation of stoichiometric metal- or halogen-containing chemical wastes. A wide range of aromatic esters, including hetarenes and pharmaceutical molecules, can be converted into aryl nitriles.
- Iizumi, Keiichiro,Kurosawa, Miki B.,Isshiki, Ryota,Muto, Kei,Yamaguchi, Junichiro
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supporting information
p. 1555 - 1559
(2020/11/10)
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- Method for synthesizing biphenyl compound by taking phenol as raw material
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The invention discloses a method for synthesizing a biphenyl compound by using phenol as a raw material in the technical field of organic chemical synthesis, which comprises the following steps: carrying out a mixed reaction process on phenol or substituted phenol, alkali and 50-90% ethanol aqueous solution, slowly introducing sulfonyl fluoride gas, and carrying out magnetic stirring reaction at normal temperature for 4-12 hours, adding arylboronic acid, alkali and a palladium catalyst into a round-bottom flask, continuing to react for 6-12 hours at normal temperature, after the reaction is finished, adding a saturated edible salt solution into the round-bottom flask, carrying out a water quenching reaction process to obtain a reaction mixture, extracting a reaction product from the reaction mixture by using ethyl acetate, combining organic phases, concentrating filtrate, and separating the concentrated filtrate by using column chromatography to obtain analytically pure biphenyl or terphenyl compounds. By using the method, on one hand, the production cost of the biphenyl compound is reduced, and on the other hand, the method also has a wide application prospect in the aspects of synthesis of natural products, medicines, pesticides, herbicides, polymer conduction materials, liquid crystal materials and the like.
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Paragraph 0074-0076
(2020/07/15)
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- Method for synthesizing biphenyl compound by taking suaeda salsa extract liquor as solvent
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The invention discloses a method for synthesizing a biphenyl compound by using suaeda salsa extract as a solvent in the technical field of organic chemical synthesis, which comprises the following steps: roasting suaeda salsa in a muffle furnace to obtain ash, dissolving the ash in distilled water, refluxing, cooling the solution, and filtering to obtain a faint yellow solution which is the suaedasalsa extract liquor; sequentially adding 1mmol of aryl halide, 1.1mmol of arylboronic acid, 0.001mmol to 0.01mmol of a catalyst and 4ml of the suaeda salsa extract liquor into a round-bottom flask,stirring at 100 DEG C to react for 2 hours, cooling the reactant to room temperature, filtering, mixing the obtained filter residue with a palladium catalyst to obtain a mixture; and dissolving the mixture in ethyl acetate, filtering to remove the palladium catalyst, and drying the filtrate by distillation to obtain the biphenyl compound. According to the scheme, a phosphine ligand, alkali and anadditive do not need to be added, a Suzuki reaction system with biomass extract as a reaction medium is adopted, and a green, simple, convenient and efficient method is provided for synthesizing biphenyl compounds.
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Paragraph 0053-0054
(2020/06/30)
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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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- Invisible Chelating Effect Exhibited between Carbodicarbene and Phosphine through π-π Interaction and Implication in the Cross-Coupling Reaction
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Palladium complexes supported with the mixed ligands carbodicarbene (CDC) and different phosphine ligands (PPh3, PTol3, and PCy3) were prepared, and their molecular structures were characterized. Examination of the structures of 2-PPh3 and 2-PTol3 with cis configuration discloses the existence of an unexpected π-π interaction between one phenyl group of the phosphine and the benzimidazole ring of a CDC. The palladium complex 2-PPh3 is an active Suzuki-Miyaura catalyst with a wide scope of substrates containing various functional groups and steric demands. In contrast to electron-withdrawing aryl bromide, the yield of product for electron-rich substrates was improved by adding a catalytic amount of DMSO under aerobic conditions. The solution NMR and structural analysis has revealed that the intramolecular π-π interaction between CDC and phosphine ligands has a positive influence on the activity of the reaction, which is further supported by quantum chemical calculations.
- Shih, Wei-Chih,Chiang, Yun-Ting,Wang, Qing,Wu, Ming-Chun,Yap, Glenn P. A.,Zhao, Lili,Ong, Tiow-Gan
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supporting information
p. 4287 - 4297
(2017/11/20)
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- Polymer biquinolyl-containing complexes of Pd(ii) as efficient catalysts for cyanation of aryl and vinyl halides with K4Fe(CN)6
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A catalytic system for cyanation of aryl and vinyl halides with K4Fe(CN)6 based on a structurally tunable and nontoxic polymer backbone of polyamic type with biquinolyl fragments in the polymer chain capable of coordination to PdII ions is developed. The catalyst is eligible for thermal and microwave activation; in the latter case the reaction time is dramatically decreased. Cyanation of vinyl bromides occurs stereoselectively, and the configuration of the starting alkene is retained; even for Z-isomers the impact of configuration inversion is less than 5%. The polymer-based Pd catalyst is applicable for one-pot multi-step synthesis of the precursors of mesogenic structures of biphenyl type. Consecutive cross-coupling and cyanation reactions can be performed in the presence of the same portion of catalyst, in the same solvent, without isolation of intermediate products.
- Nikitin, Oleg M.,Polyakova, Olga V.,Sazonov, Petr K.,Yakimansky, Alexander V.,Goikhman, Mikhail Ya.,Podeshvo, Irina V.,Magdesieva, Tatiana V.
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p. 10465 - 10473
(2016/12/07)
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- Self-assembled Pd6L4 cage and Pd4L4 square using hydrazide based ligands: Synthesis, characterization and catalytic activity in Suzuki-Miyaura coupling reactions
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A discrete Pd6L4Td-symmetric molecular cage and a discrete Pd4L4 square assembly were obtained using a coordination-driven self-assembly technique. The assembly, Pd6L4, was prepared via a face-directed method, utilising a 'cis-clipped' palladium(ii) species and a new C3 symmetric tripodal hydrazinic ligand. The Pd4L4 square assembly was prepared via an edge directed method, using the 'cis-clipped'-palladium(ii) species and a new C2 symmetric dipodal hydrazinic ligand. Both assemblies were characterised using multinuclear NMR and ESI-MS spectroscopic techniques and elemental analysis. The size of the assemblies were assigned from HR-TEM measurements, while DOSY NMR analysis established the presence of single component species in solution. Optimised structures obtained using Hartree-Fock calculations are in conformity with the experimental results. Both the assemblies show significant catalytic activity as heterogeneous catalysts for Suzuki-Miyaura coupling reactions under mild, aerobic and phosphine free conditions in aqueous ethanolic medium.
- Pradhan, Subhashis,John, Rohith P.
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p. 12453 - 12460
(2016/02/12)
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- Expedient Preparation of Aryllithium and Arylzinc Reagents from Aryl Chlorides Using Lithium 4,4′-Di- tert -Butylbiphenylide and Zinc(II) Chloride
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We report an efficient method for the preparation of aryllithium and zinc reagents from inexpensive and readily available aryl chlorides by using lithium 4,4′-di-tert-butylbiphenylide (LiDBB) as a lithiation reagent. The resulting organometallic reagents underwent subsequent reactions with a variety of electrophiles, such as an aldehydes, DMF, PhSSO2Ph, TsCN, an aryl halide, or an acid chloride (through Pd-catalyzed cross-coupling). Aryl chlorides bearing substituents, including methoxy, 3,4-methylenedioxy, fluoride, TMS, OTMS, NMe2, acetal, and ketal, were shown to be appropriate substrates. Interestingly, aryl chlorides containing a formyl group could also be used, provided that the formyl group was temporarily converted into an α-amino alkoxide by using the lithium amide of N,N,N′-trimethylethylenediamine (LiTMDA). The presence of a hydroxyl group was also tolerated when it was deprotonated with n-BuLi prior to the addition of LiDBB.
- Shen, Zhi-Liang,Sommer, Korbinian,Knochel, Paul
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p. 2617 - 2630
(2015/09/01)
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- A ligand-free palladium-catalyzed cross-coupling of aryl sulfinates with aryl bromides
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A ligand-free Pd-catalyzed cross-coupling of aryl sulfinates with aryl bromides has been developed. A variety of aryl bromides and aryl sulfinates undergo this transformation to yield the desired biaryl in a practical and economical manner. Georg Thieme Verlag Stuttgart New York.
- Ortgies, Dirk H.,Forgione, Pat
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p. 1715 - 1721
(2013/09/02)
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- One-by-one hydrogenation, cross-coupling reaction, and Knoevenagel condensations catalyzed by PdCl2 and the downstream palladium residue
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A novel catalyst-economic strategy with a recovered palladium catalyst was successfully applied for multi-task and maximum reuse in different types of one-by-one downstream reactions, from catalytic hydrogenation to Suzuki and Sonogashira-type cross-coupling reactions, Knoevenagel condensations, and trans-Knoevenagel-like condensations.
- Wang, Hu,Li, Li,Bai, Xing-Feng,Deng, Wen-Hui,Zheng, Zhan-Jiang,Yang, Ke-Fang,Xu, Li-Wen
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supporting information
p. 2349 - 2355
(2013/09/12)
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- An efficient and simple protocol for a PdCl2-ligandless and additive-free Suzuki coupling reaction of aryl bromides
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A highly efficient, convenient, and environmentally friendly protocol was developed for the PdCl2-catalyzed ligandless and additive-free Suzuki reaction of aryl bromides with arylboronic acids in water/ethanol.
- Qiu, Jun,Wang, Limin,Liu, Mingtao,Shen, Qiang,Tang, Jun
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supporting information; experimental part
p. 6489 - 6491
(2011/12/16)
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