- CuI in biorenewable basic medium: Three novel and low E-factor Suzuki-Miyaura cross-coupling reactions
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In this article, we have disclosed three inexpensive and novel copper-catalyzed C(sp2)–C(sp2) coupling reactions of substituted aryl/heteroaryl halides with arylboronic acids by employing water extract of pomegranate ash (WEPA) as biorenewable base and aqueous reaction medium. CuI/WEPA, CuI/WEPA/DABCO, CuI/WEPA/SPhos catalytic systems were developed for the present Suzuki-Miyaura coupling. WEPA has been found to be the effective base and reaction medium for copper-catalysed Suzuki-Miyaura reactions with and without ligands to provide good to high yields of coupling products. This method has remarkable advantages like inexpensive and waste-derived biorenewable base, low catalyst loading, moderate temperature, replacement of precious palladium with abundant copper, no or negligible contamination of copper in products, low E-factor, high chemoselectivity and a large substrate scope.
- Lakshmidevi, Jangam,Naidu, Bandameeda Ramesh,Venkateswarlu, Katta
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- Photoredox Cyclization of N-Arylacrylamides for Synthesis of Dihydroquinolinones
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Metal- and additive-free photoredox cyclization of N-arylacrylamides is herein reported that provides a concise access to the formation of dihydroquinolinones. In this protocol, sustainable visible light was used as the energy source, and the organic light-emitting molecule 4CzIPN served as the efficient photocatalyst. This reaction system features exclusive 6-endo-trig cyclization selectivity with a generally good yield of a range of functionalized dihydroquinolinones and dihydrobenzoquinolinones. Mechanistical studies reveal the feasibility of both 1,3-H shift and intersystem crossing of the diradical intermediate.
- Liu, Zhaosheng,Zhong, Shuai,Ji, Xiaochen,Deng, Guo-Jun,Huang, Huawen
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supporting information
p. 349 - 353
(2021/12/27)
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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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- 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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- NOVEL HYDRAZONE DERIVATIVE WITH ARYL OR HETEROARYL GROUP SUBSTITUTED AT TERMINAL AMINE GROUP THEREOF AND USE THEREOF
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The present invention relates to novel hydrazone derivatives in which a terminal amine group is substituted with an aryl group or a heteroaryl group, and uses thereof.
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Paragraph 0069; 0095
(2021/11/04)
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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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- Heterogeneous Fe3O4@Si–NHC–Pd Catalyst: Synthesis, Characterization, and Catalytic Activity in the Suzuki–Miyaura Cross-Coupling Reaction under Mild Conditions
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Abstract: A novel Fe3O4@Si–NHC–Pd catalystwith N-heterocyclic carbenes (NHCs) moiety as an alternative ligand tophosphines for metal complexes has been synthesized and characterized by variousmethods. Synthesis of metal nanoparticles has been accomplished withoutaggregation, and the prepared catalyst has been applied in theSuzuki–Miyauracross-coupling reaction of boronic acids and aryl halides in water usingEt3N as a base. The catalyst has demonstrated highefficiency at room temperature and can be easily removed from the reaction mediausing an external magnetic field and recycled at least five times withoutsignificant decrease of its activity.
- Kalishomi, R. Ghavidel,Rostamizadeh, S.
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p. 1140 - 1146
(2021/08/06)
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- Cu(OAc)2 entrapped on ethylene glycol-modified melamine–formaldehyde polymer as an efficient heterogeneous catalyst for Suzuki–Miyaura coupling reactions
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This work is described as an environmental friendly approach for Cu(OAc)2 entrapped on ethylene glycol-modified melamine–formaldehyde-based polymeric material (Cu@MCOP) which has been successfully synthesized by simple approaches using commercially available starting materials via solvothermal techniques and without using any toxic reagents and chemicals. The structural, morphological, physicochemical characteristics and catalytic activity of the heterogeneous catalyst (Cu@MCOP) were analyzed by various instrumental methods including powder X-ray diffraction, FT-IR, UV-DRS, X-ray photoelectron spectroscopy, SEM and elemental mapping which have been used to authenticate the polymeric materials Cu@MCOP. The catalytic performance of Cu@MCOP as solid heterogeneous catalyst was evaluated in synthesis of various biphenyl derivatives through Suzuki–Miyaura cross-coupling reactions of various aryl halides with substituted organoboranes under normal reaction conditions. Furthermore, the copper catalyst was easily available, low cost, cheap and best instead of palladium, which shows good catalytic activity and excellent yield (up to 86%); the catalyst can be separated easily and recycled for more than five times. Graphic abstract: [Figure not available: see fulltext.].
- Sadhasivam, Velu,Sankar, Balakrishnan,Elamathi, Ganesan,Mariyappan, Mathappan,Siva, Ayyanar
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p. 681 - 700
(2019/11/03)
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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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- Novel hydrazone derivatives comprising aryl or heteroaryl group substituted at terminal amine and use thereof
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The present invention relates to novel hydrazone derivatives with an aryl or heteroaryl group substituted at a terminal amine group thereof and a use thereof.
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Paragraph 0325; 0327; 0328; 0455; 0457; 0458
(2020/08/28)
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- Base-Promoted Aerobic Oxidation/Homolytic Aromatic Substitution Cascade toward the Synthesis of Phenanthridines
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The current protocol represents a transition metal-free synthesis of polysubstituted phenanthridines from abundant starting materials like benzhydrol and 2-iodoaniline derivatives. The reaction involves sequential oxidation of alcohol and direct condensation reaction with the amine resulting in a C?N bond formation followed by a radical C?C coupling in a cascade sequence. The used base potassium tert-butoxide plays a dual role in dehydrogenation and homolytic aromatic substitution reaction. Using this methodology, twenty substituted phenanthridine derivatives were synthesized with up to 85% isolated yield. (Figure presented.).
- Maiti, Debabrata,Halder, Atreyee,De Sarkar, Suman
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supporting information
p. 4941 - 4948
(2019/11/03)
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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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- METHOD OF MAKING NANOMETER THIN SHEETS OF METALS IN AIR
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The present invention relates to an ambient ion based method of making free-standing 2D metal sheets made of bare NPs, at the air-liquid interface. An electro-hydrodynamic flow field was generated by electrospray deposition on the liquid surface, which in turn assisted the assembly of the NPs. The NP-NSs were made under ambient conditions at room temperature from metal salt precursors. The sheets can be made of different elements such as Pd, Au, and Ag. Synthesized 2D NP-NSs were used as efficient and reusable heterogeneous catalysts for C-C bond formation reactions. These thin metal sheets may also be used as catalysts, sensors, gas adsorbing media, electrodes for electrochemical reactions, etc.
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Page/Page column 8; 9
(2019/05/02)
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- Base-Free Suzuki–Miyaura Coupling Reaction Using Palladium(II) Supported Catalyst in Water
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Abstract: The carbon–carbon bond formation via Suzuki–Miyaura reaction was performed in water as green solvent. Pd(OAc)2(PPh3)2 supported on magnesium hydroxide and cerium carbonate hydroxide composite was prepared and characterized by various techniques. The cross-coupling reaction of aryl halides carried out in water using mild conditions. The effects of temperature, solvents, the amount of catalyst and leaving groups were studied to find the optimization conditions for cross-coupling reaction. Various aryl halides were smoothly transformed into the biaryls in good yields. In addition, the catalyst also exhibited stability and catalytic performance in the cross-coupling of aryl halides. Graphical Abstract: [Figure not available: see fulltext.] A new approach is developed for carbon–carbon bond formation via Suzuki–Miyaura reaction.2 Pd(OAc)2(PPh3)2?supported on mixed magnesium hydroxide and cerium carbonate hydroxide were prepared and characterized by XRD, XPS, SEM–EDX techniques. The cross-coupling reaction of aryl halides can be carried out in water and under mild conditions (80 °C).
- Tomar, Ravi,Singh, Nidhi,Kumar, Neeraj,Tomar, Vartika,Chandra, Ramesh
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- De novo design approaches targeting an envelope protein pocket to identify small molecules against dengue virus
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Dengue fever is a mosquito-borne viral disease that has become a major public health concern worldwide. This disease presents with a wide range of clinical manifestations, from a mild cold-like illness to the more serious hemorrhagic dengue fever and dengue shock syndrome. Currently, neither an approved drug nor an effective vaccine for the treatment are available to fight the disease. The envelope protein (E) is a major component of the virion surface. This protein plays a key role during the viral entry process, constituting an attractive target for the development of antiviral drugs. The crystal structure of the E protein reveals the existence of a hydrophobic pocket occupied by the detergent n-octyl-β-d-glucoside (β-OG). This pocket lies at the hinge region between domains I and II and is important for the low pH-triggered conformational rearrangement required for the fusion of the virion with the host's cell. Aiming at the design of novel molecules which bind to E and act as virus entry inhibitors, we undertook a de novo design approach by “growing” molecules inside the hydrophobic site (β-OG). From more than 240000 small-molecules generated, the 2,4 pyrimidine scaffold was selected as the best candidate, from which one synthesized compound displayed micromolar activity. Molecular dynamics-based optimization was performed on this hit, and thirty derivatives were designed in silico, synthesized and evaluated on their capacity to inhibit dengue virus entry into the host cell. Four compounds were found to be potent antiviral compounds in the low-micromolar range. The assessment of drug-like physicochemical and in vitro pharmacokinetic properties revealed that compounds 3e and 3h presented acceptable solubility values and were stable in mouse plasma, simulated gastric fluid, simulated intestinal fluid, and phosphate buffered saline solution.
- Acosta Dávila, John Alejandro,Adler, Natalia S.,Aucar, Maria G.,Battini, Leandro,Bollini, Mariela,Cavasotto, Claudio N.,Cordo, Sandra M.,Fernández, Gabriela A.,Gamarnik, Andrea V.,García, Cybele C.,Gebhard, Leopoldo G.,Hernández de los Ríos, Alejandro,Leal, Emilse S.,Monge, María Eugenia,Morell, María L.,Videla, Mariela
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supporting information
(2019/08/30)
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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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- Chemoselective reduction of nitroarenes with hydrazine over a highly active alumina-supported cobalt nanocatalyst
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A green and efficient procedure is reported for the chemoselective reduction of nitroarenes catalyzed by a highly active alumina-supported cobalt nanocatalyst in the presence of hydrazine hydrate. The nanocatalyst can be applied under mild reflux conditions for the synthesis of arlyamines in high yields. Moreover, the catalyst can be easily recovered by simple filtration and reused several times without obvious loss in its catalytic activity.
- Albadi, Jalal,Samimi, Heshmat Allah,Jalali, Mehdi
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p. 740 - 744
(2019/10/14)
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- Preparation and Characterization of an Efficient Nano-Inorganic Composite of CuO/ZnO/Al2O3 for the Catalytic Amination of Aryl Halides in Aqueous Conditions
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In this research, an efficient recyclable nano-inorganic composite of CuO/ZnO/Al2O3 (CuO/ZnO/Al2O3 nanocatalyst) is prepared, characterized and used for the amination of aryl halides with aqueous ammonia in water. The catalyst was prepared by co-precipitation method and characterized by various techniques such as the X-ray diffraction, scanning electron microscope, energy dispersive spectroscopy, and brunauer–Emmett–Teller surface area analysis. Various aryl halides reacted with aqueous ammonia and corresponding products were obtained in high yields. CuO/ZnO/Al2O3 nanocatalyst as an efficient stable catalyst is recyclable up to five consecutive runs by simple filtration. Graphical Abstract: An efficient recyclable nano-inorganic composite of CuO/ZnO/Al2O3 (CuO/ZnO-Al2O3 nanocatalyst) is prepared, characterized and used for the amination of aryl halides with aqueous ammonia in water. [Figure not available: see fulltext.].
- albadi, Jalal,Jalali, Mehdi,Samimi, Heshmat Allah
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p. 3750 - 3756
(2018/10/15)
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- Metallacycle-Cored Supramolecular Polymers: Fluorescence Tuning by Variation of Substituents
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Herein, we present a method for the preparation of supramolecular polymers with tunable fluorescence via the combination of metal-ligand coordination and phenanthrene-21-crown-7 (P21C7)-based host-guest interactions. A suite of rhomboidal metallacycles wi
- Xu, Luonan,Shen, Xi,Zhou, Zhixuan,He, Tian,Zhang, Jinjin,Qiu, Huayu,Saha, Manik Lal,Yin, Shouchun,Stang, Peter J.
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supporting information
p. 16920 - 16924
(2018/12/14)
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- AMINATION AND HYDROXYLATION OF ARYLMETAL COMPOUNDS
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In one aspect, the present disclosure provides methods of preparing a primary or secondary amine and hydroxylated aromatic compounds. In some embodiments, the aromatic compound may be unsubstituted, substituted, or contain one or more heteroatoms within the rings of the aromatic compound. The methods described herein may be carried out without the need for transition metal catalysts or harsh reaction conditions.
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Paragraph 0098; 0134; 0135; 0158
(2018/03/25)
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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 5-methyl-2-phenylphenanthridium derivatives as FtsZ-targeting antibacterial agents from structural simplification of natural product sanguinarine
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A novel series of 5-methyl-2-phenylphenanthridium derivatives were displayed outstanding activity against a panel of antibiotic-sensitive and -resistant bacteria strains compared with their precursor sanguinarine, ciprofloxacin and oxacillin sodium. Compounds 7 l, 7m and 7n were found to display the most effective activity against five sensitive strains (0.06–2 μg/mL) and three resistant strains (0.25–4 μg/mL). The kinetic profiles indicated that compound 7l possessed the strongest bactericidal effect on S. aureus ATCC25923, with the MBC value of 16 μg/mL. The cell morphology and the FtsZ polymerization assays indicated that these compounds inhibited the bacterial proliferation by interfering the function of bacterial FtsZ. The SARs showed that all the 4-methyl-substituted 5-methyl-2-phenylphenanthridium subseries could be further investigated as the FtsZ-targeting antibacterial agents.
- Liu, Jingru,Ma, Ruxin,Bi, Fangchao,Zhang, Fa,Hu, Chaoyu,Venter, Henrietta,Semple, Susan J.,Ma, Shutao
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supporting information
p. 1825 - 1831
(2018/04/16)
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- Rapid heteroatom transfer to arylmetals utilizing multifunctional reagent scaffolds
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Arylmetals are highly valuable carbon nucleophiles that are readily and inexpensively prepared from aryl halides or arenes and widely used on both laboratory and industrial scales to react directly with a wide range of electrophiles. Although C-C bond formation has been a staple of organic synthesis, the direct transfer of primary amino (-NH2) and hydroxyl (-OH) groups to arylmetals in a scalable and environmentally friendly fashion remains a formidable synthetic challenge because of the absence of suitable heteroatom-transfer reagents. Here, we demonstrate the use of bench-stable N-H and N-alkyl oxaziridines derived from readily available terpenoid scaffolds as efficient multifunctional reagents for the direct primary amination and hydroxylation of structurally diverse aryl- and heteroarylmetals. This practical and scalable method provides one-step synthetic access to primary anilines and phenols at low temperature and avoids the use of transition-metal catalysts, ligands and additives, nitrogen-protecting groups, excess reagents and harsh workup conditions.
- Gao, Hongyin,Zhou, Zhe,Kwon, Doo-Hyun,Coombs, James,Jones, Steven,Behnke, Nicole Erin,Ess, Daniel H.,Kürti, László
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p. 681 - 688
(2017/06/30)
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- Method for synthesizing 2,4-dichloro-6-p-methylphenyl quinoline
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The invention belongs to the technical field of organic electrofluorescent materials, and discloses a method for synthesizing 2,4-dichloro-6-p-methylphenyl quinolone. The method comprises the following steps: performing a Suzuki coupling reaction on 4-met
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- Highly bulky and stable geometry-constrained iminopyridines: Synthesis, structure and application in Pd-catalyzed Suzuki coupling of aryl chlorides
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A series of bulky geometry-constrained iminopyridylpalladium chlorides were developed. The steric environment adjacent to the nitrogen atom in the pyridine rings and diimine parts enhanced the thermal stability of the palladium species. Bulkier groups at the imino group stabilized the palladium species and the corresponding palladium chlorides showed high activities in the coupling reaction of aryl chlorides.
- Lai, Yi,Zong, Zhijian,Tang, Yujie,Mo, Weimin,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu,Jin, Liqun,Sun, Wen-Hua,Hu, Xinquan
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p. 213 - 221
(2017/02/15)
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- Mechanism insight and scope of PEPPSI-catalyzed cross-coupling reaction between triarylbismuth and arylbromide
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In this paper we report the first cross-coupling reaction of Ar3Bi with Ar'X mediated by Pd-NHC complexes by keeping the ability of Ar3Bi to transfer the three aryl moieties. Investigations were carried out in order to minimize the quantity of the side product Ar-Ar coming from the conversion of Ar3Bi. The results showed that PEPPSI IPr was a good catalyst precursor. Efforts were focussed on the rule of each additive such as PPh3 and the base. It was notably found that the presence of PPh3 (ratio PEPPSI IPr/PPh3: 1/1) was essential to keep the process efficient. Therefore NHC-Pd-PPh3 has been assumed as being the catalytic species. Under the optimized reaction conditions the concomitant formation of the undesired biaryl side product was restricted to its inherent formation consecutive to the reduction of the catalyst precursor to Pd(0). In a last study, the scope and the limitation of the new catalytic methodology were examined and a large range of unsymmetrical biaryl compounds Ar-Ar’ bearing various substituents from strongly electron-donating to electron-withdrawing ones have been prepared and fully characterized.
- Cassirame, Bénédicte,Condon, Sylvie,Pichon, Christophe
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- 3-Hydroxypyrimidine-2,4-diones as Selective Active Site Inhibitors of HIV Reverse Transcriptase-Associated RNase H: Design, Synthesis, and Biochemical Evaluations
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Human immunodeficiency virus (HIV) reverse transcriptase (RT) associated ribonuclease H (RNase H) remains an unvalidated antiviral target. A major challenge of specifically targeting HIV RNase H arises from the general lack of selectivity over RT polymerase (pol) and integrase (IN) strand transfer (ST) inhibitions. We report herein the synthesis and biochemical evaluations of three novel 3-hydroxypyrimidine-2,4-dione (HPD) subtypes carefully designed to achieve selective RNase H inhibition. Biochemical studies showed the two subtypes with an N-1 methyl group (9 and 10) inhibited RNase H in low micromolar range without siginificantly inhibiting RT polymerase, whereas the N-1 unsubstituted subtype 11 inhibited RNase H in submicromolar range and RT polymerase in low micromolar range. Subtype 11 also exhibited substantially reduced inhibition in the HIV-1 INST assay and no significant cytotoxicity in the cell viability assay, suggesting that it may be amenable to further structure-activity relationship (SAR) for identifying RNase H inhibitors with antiviral activity.
- Tang, Jing,Liu, Feng,Nagy, Eva,Miller, Lena,Kirby, Karen A.,Wilson, Daniel J.,Wu, Bulan,Sarafianos, Stefan G.,Parniak, Michael A.,Wang, Zhengqiang
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p. 2648 - 2659
(2016/04/10)
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- Nickel-catalyzed monoarylation of ammonia
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Structurally diverse (hetero)aryl chloride, bromide, and tosylate electrophiles were employed in the Ni-catalyzed monoarylation of ammonia, including chemoselective transformations. The employed JosiPhos/[Ni(cod)2] catalyst system enables the use of commercially available stock solutions of ammonia, or the use of ammonia gas in these reactions, thereby demonstrating the versatility and potential scalability of the reported protocol. Proof-of-principle experiments established that air-stable [(JosiPhos)NiCl2] precatalysts can be employed successfully in such transformations. Lighten Up: The substrate scope of the title reaction includes (hetero)aryl chloride, bromide, and tosylate electrophiles. The versatility and potential scalability of the reported method is demonstrated by the use of either commercially available stock solutions of ammonia or ammonia gas.
- Borzenko, Andrey,Rotta-Loria, Nicolas L.,Macqueen, Preston M.,Lavoie, Christopher M.,McDonald, Robert,Stradiotto, Mark
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supporting information
p. 3773 - 3777
(2015/03/18)
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- Miniaturized catalysis: monolithic, highly porous, large surface area capillary flow reactors constructed in situ from polyhedral oligomeric silsesquioxanes (POSS)
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A single-step molding process utilizing free-radical cross-linking reaction of vinyl POSS in microliter-sized dimensions leads to hierarchically-structured, mechanically robust, porous hybrid structures. Functional variants show excellent performance in Suzuki-type coupling reactions. Due to their small volume, long-term operational robustness, and potential chemical diversity, these materials are promising candidates for catalyst screening applications.
- Scholder,Nischang
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p. 3917 - 3921
(2015/08/03)
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- Palladium nanoparticles in catalytic carbon nanoreactors: The effect of confinement on Suzuki-Miyaura reactions
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We explore the construction and performance of a range of catalytic nanoreactors based on palladium nanoparticles encapsulated in hollow graphitised nanofibres. The optimum catalytic material, with small palladium nanoparticles located almost exclusively at the graphitic step-edges within nanoreactors, exhibits attractive catalytic properties in Suzuki-Miyaura cross-coupling reactions. Confinement of nanoparticles at the step-edges facilitates retention of catalytic centres and recycling of catalytic nanoreactors without any significant loss of activity or selectivity over multiple catalytic cycles. Furthermore, careful comparison of the catalytic properties of palladium nanoparticles either on or in nanoreactors reveals that nanoscale confinement of catalysts fundamentally affects the pathways of the Suzuki-Miyaura reaction, with the yield and selectivity for the cross-coupled product critically dependent on the steric properties of the aryl iodide reactant, whereas no effects of confinement are observed for aryl boronic acid reactants possessing substituents in different positions. These results indicate that the oxidative addition step of the Suzuki-Miyaura reaction occurs at the step-edge of nanofibres, where the mechanisms and kinetics of chemical reactions are known to be sensitive to nanoscale confinement, and thus the extent of confinement in carbon nanoreactors can be discretely controlled by careful selection of the aryl iodide reactant.
- Cornelio,Saunders,Solomonsz,Laronze-Cochard,Fontana,Sapi,Khlobystov,Rance
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supporting information
p. 3918 - 3927
(2015/02/19)
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- Dendrimer-encapsulated Pd nanoparticles as catalysts for C-C cross-couplings in flow microreactors
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The inner walls of glass microreactors were functionalized with dendrimer-encapsulated Pd nanoparticles. The catalysts were efficient for the Heck-Cassar (copper-free Sonogashira) and Suzuki-Miyaura (SMC) cross-coupling reactions. For the Heck-Cassar reaction between iodobenzene and phenylacetylene, the catalytic system exhibited a high turnover frequency (TOF) and on average required milder reaction conditions as compared to other continuous flow cross-couplings. A study of the substituent effect of para-substituted aryl halides revealed a beneficial effect of electron-withdrawing side groups for the SMC. Moreover, a reaction constant (ρ) of 1.5, determined from the Hammett plot, indicated a possible rate-determining step other than the oxidative addition.
- Ricciardi, Roberto,Huskens, Jurriaan,Verboom, Willem
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p. 4953 - 4959
(2015/05/05)
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- Structure-activity relationship study of E6 as a novel necroptosis inducer
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Necroptosis inducers represent a promising potential treatment for drug-resistant cancer. We herein describe the structure modification of E6, which was identified recently as a potent and selective necroptosis inducer. The studies described herein demonstrate for the first time that functionalized biphenyl derivatives possess necroptosis inducer activity. Furthermore, these studies have led to the identification of two promising compounds (5h and 5j) that can be used for further optimization studies as well as mechanism of action investigations.
- Mou, Jianfeng,Park, Ann,Cai, Yu,Yuan, Junying,Yuan, Chengye
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supporting information
p. 3057 - 3061
(2015/06/22)
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- Palladium supported on hollow magnetic mesoporous spheres: A recoverable catalyst for hydrogenation and Suzuki reaction
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A high-performance palladium catalyst was developed by the covalent binding of a Schiff base ligand, N,N′-bis(3-salicylidenaminopropyl)amine (salpr), on the surface of hollow magnetic mesoporous spheres (HMMS) followed by immobilization with Pd(0). The catalyst was characterized by TEM, EDX, FT-IR, XRD, VSM, TGA and N2 adsorption-desorption. The novel catalyst exhibited high activity in hydrogenation and Suzuki coupling reaction. Furthermore, it could be recovered from the reaction mixture in a facile manner and recycled six times without any loss of activity.
- Liu, Hengzhi,Wang, Peng,Yang, Honglei,Niu, Jianrui,Ma, Jiantai
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p. 4343 - 4350
(2015/06/16)
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- Pd Nanoparticles Immobilized on Orange-Like Magnetic Polymer-Supported Fe3O4/PPy Nanocomposites: A Novel and Highly Active Catalyst for Suzuki Reaction in Water
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An orange-like catalyst of Pd nanoparticles supported by magnetic Fe3O4/polypyrrole nanocomposite is facilely prepared. It shows great activity for Suzuki coupling reactions in neat water under atmospheric pressure. This magnetic and water-soluble catalyst avoids the use of toxic solvents in traditional process of coupling reactions and can be easily recovered by mean of a convenient magnetic separation technique, demonstrating in both environmental friendliness and recyclability.
- Sun, Xun,Zheng, Yuhua,Sun, Libo,Su, Huijuan,Qi, Caixia
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p. 1047 - 1053
(2015/01/30)
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- N-heterocyclic carbene-assisted, Bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates
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Efficient bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates have been effected with an assistance of N-heterocyclic carbene (NHC) generated in situ from N,N′-dialkylimidazoliums, e.g., N-butyl-N′-methylimidazolium bromide ([Bmim]Br), in toluene using K3PO4·3H2O as base. In contrast to bis(NHC)nickel-catalyzed conventional Suzuki coupling of arylboronic acids, mono(NHC)bis(phosphine)nickel species generated in situ from Ni(PPh3)2Cl2/[Bmim]Br displayed high catalytic activities in the cross-couplings of diarylborinic acids. The structural influences from diarylborinic acids were found to be rather small, while electronic factors from aryl chlorides, tosylates, and sulfamates affected the couplings remarkably. The couplings of electronically activated aryl chlorides, tosylates, and sulfamates could be efficiently effected with 1.5 mol % NiCl2(PPh3)2/[Bmim]Br as catalyst precursor to give the biaryl products in excellent yields, while 3-5 mol % loadings had to be used for the couplings of non- and deactivated ones. A small ortho-substitutent on the aromatic ring of aryl chlorides, tosylates, and sulfamates was tolerable. Applicability of the nickel-catalyzed cross-couplings in practical synthesis of fine chemicals has been demonstrated in process development for a third-generation topical retinoid, Adapalene.
- Ke, Haihua,Chen, Xiaofeng,Zou, Gang
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p. 7132 - 7140
(2014/08/18)
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- Nickel-catalyzed cross-coupling of diarylborinic acids with aryl chlorides
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A highly efficient nickel/triarylphosphine catalyst system, Ni[P(4-MeOPh)3]2Cl2/2P(4-MeOPh)3, has been developed for cross-coupling of diarylborinic acids with a wide range of aryl chlorides. A variety of unsymmetrical biaryl and heterobiaryl compounds with various functional groups and steric hindrance could be obtained in good to excellent yields using 0.5-2 mol % catalyst loadings in the presence of K 3PO4·3H2O in toluene. The high atom economy of diarylborinic acids and cost-effectiveness of the nickel/phosphine catalyst system make the cross-coupling truly practical in the production of biaryl fine chemicals. Usefulness of the nickel/phosphine catalyzed cross-coupling of diarylborinic acids with aryl chlorides has been demonstrated in the development of a scalable and economical process for synthesis of 4′-methyl-2-cyanobiphenyl, Sartan biphenyl.
- Chen, Xiaofeng,Ke, Haihua,Zou, Gang
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p. 379 - 385
(2014/03/21)
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- An emerging reactor technology for chemical synthesis: Surface acoustic wave-assisted closed-vessel Suzuki coupling reactions
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In this paper we demonstrate the use of an energy-efficient surface acoustic wave (SAW) device for driving closed-vessel SAW-assisted (CVSAW), ligand-free Suzuki couplings in aqueous media. The reactions were carried out on a mmolar scale with low to ultr
- Kulkarni, Ketav,Friend, James,Yeo, Leslie,Perlmutter, Patrick
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p. 1305 - 1309
(2014/04/03)
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- Suzuki coupling reaction catalyzed heterogeneously by Pd(salen)/ polyoxometalate compound: Another example for synergistic effect of organic/inorganic hybrid
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A hybrid compound consisting of palladium(salen) [salen = N,N′-bis(salicylidene)ethylenediamine] complex covalently linked to a lacunary Keggin-type polyoxometalate, K8[SiW11O 39](POM), was synthesized and characterized by FT-IR, elemental analysis, inductively coupled plasma and diffuse reflectance UV-visible spectroscopic methods. The hybrid, [Pd(salen)-POM], was investigated in the Suzuki cross-coupling in EtOH/H2O under mild reaction conditions. In comparison to the corresponding organic and inorganic moiety, the hybrid has shown greatly improved catalytic activity, and much higher yields toward coupling products were obtained with a low catalyst loading for various aryl halides, including unreactive and sterically hindered ones. The catalyst also exhibited prominent recyclable performance and no obvious loss of activity was observed after six consecutive runs.
- Tong, Jinhui,Wang, Haiyan,Cai, Xiaodong,Zhang, Qianping,Ma, Hengchang,Lei, Ziqiang
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- Stabilizing PdII on hollow magnetic mesoporous spheres: A highly active and recyclable catalyst for carbonylative cross-coupling and Suzuki coupling reactions
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A hollow magnetic mesoporous silica sphere (HMMS) catalyst has been synthesized using polystyrene microspheres as a chemical template. The catalyst was characterized by TEM, XRD, XPS and vibrating sample magnetometry (VSM). The catalyst shows high activity for the carbonylative cross-coupling reaction of aryl iodides with arylboronic acids and Suzuki coupling reactions. The newly developed catalyst is easy to recover by magnetic separation from the liquid phase of the reaction and can be recycled. Importantly, the catalyst revealed high efficiency and high stability under the reaction conditions and during recycling stages.
- Niu, Jianrui,Liu, Mengmeng,Wang, Peng,Long, Yu,Xie, Miao,Li, Rong,Ma, Jiantai
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p. 1471 - 1476
(2014/05/06)
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- PVC-supported palladium nanoparticles: An efficient catalyst for suzuki cross-coupling reactions at room temperature
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A simple and efficient protocol is described for a Suzuki reaction catalyzed by poly(vinyl chloride)-supported nanoparticles of metallic palladium at room temperature. Aryl iodides, bromides, and chlorides underwent smooth Suzuki reactions in aqueous ethanol, an environmentally friendly solvent, under ligand-free conditions to give good yields of the desired biaryl products. The heterogeneous catalyst could be used up to four times with no detectable metal leaching or loss of catalytic efficiency. Georg Thieme Verlag Stuttgart.New York.
- Samarasimhareddy, Mamidi,Prabhu, Girish,Vishwanatha, Thimmalapura M.,Sureshbabu, Vommina V.
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p. 1201 - 1206
(2013/06/05)
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- N-Hetercocyclic carbene metallacrown ethers based on 1, 8-dihydroxy- 9, 10-anthraquinone: Synthesis, structures and application in situ palladium-catalyzed SuzukieMiyaura reaction
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N-Hetercocyclic carbene precursors containing 1,8-dihydroxy-9,10- anthraquinone derivative: 1,8-bis(3-(N-R-imidazole)propoxy)-9,10-anthraquinone 2X (L1H2: R = PhCH2, X = Br, L3H2: R = nBu, X = PF6, L4H2: R = PhCH2, X = PF6, L5H2: R = PyCH2, X = PF6), 1,8-bis(2-(N-R-imidazole)ethoxy)-9,10-anthraquinone 2X (L2H2: R = PhCH2, X = PF6) and 1,8-bis(3-(N-R-imidazole)propoxy) anthracene 2X (L6H2: R = PhCH2, X = PF6) were synthesized. N-Heterocyclic carbene metallacrown ethers: L1AgBr (1), L2AgPF 6 (2), L3AgPF6 (3), L4AgPF6 (4), L6AgPF 6 (5), L4AuPF6 (6), L5Hg(PF6)2 (7) have been prepared. Complexes 1-7 were characterized by elemental analysis, NMR spectroscopy and single crystal X-ray diffraction. Particularly, complex 4 and PdCl2(CH3CN)2 synergetically and efficiently catalyzed in situ SuzukieMiyaura cross-coupling reaction in 100% aqua-phase.
- Tang, Wei,Yuan, Wei-Guan,Zhao, Bo,Zhang, Hong-Ling,Xiong, Fang,Jing, Lin-Hai,Qin, Da-Bin
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p. 147 - 155
(2013/10/08)
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- NAPHTHALENE DERIVATIVE
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The present invention provides compounds which can regulate VCP activity. The present invention provides the compound of formula (I) (R is as defined in the description) or oxides, esters, prodrugs, pharmaceutically acceptable salts or solvates thereof. The compounds can regulate VCP activity, and thus are useful for treating VCP-mediated diseases such as neurodegenerative diseases.
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Paragraph 0580
(2013/06/27)
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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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p. 175 - 181
(2013/04/23)
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- MATRIX METALLOPROTEINASE INHIBITORS
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The present invention relates to methyl sulfonamides and N-formamides derivatives of formula (I) and to processes for their syntheses. The invention also relates to pharmacological compositions containing these derivatives and methods of treating asthma, rheumatoid arthritis, COPD, rhinitis, osteoarthritis, psoriatie arthritis, psoriasis, pulmonary fibrosis, pulmonary inflammation, acute respiratory distress syndrome, perodontitis, multiple sclerosis, gingivitis, atherosclerosis, dry eye, neointimal proliferation which leads to restenosis and ischemic heart failure, stroke, renal disease, tumor metastasis, and other inflammatory disorders characterized by over expression and over activation of an matrix metalloproteinase using the compounds.
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- Synthesis of a biphenyl library for studies of hydrogen bonding in the solid state
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A biphenyl library incorporating amide and sulfonamide groups has been synthesised via microwave-mediated Suzuki-Miyaura couplings. Many derivatives were crystallised from dichloromethane/methanol and analysed by single crystal X-ray diffraction. An inter
- Baltus, Christine B.,Press, Neil J.,Antonijevic, Milan D.,Tizzard, Graham J.,Coles, Simon J.,Spencer, John
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p. 9272 - 9277
(2012/11/07)
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- Self-assembled poly(imidazole-palladium): Highly active, reusable catalyst at parts per million to parts per billion levels
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Metalloenzymes are essential proteins with vital activity that promote high-efficiency enzymatic reactions. To ensure catalytic activity, stability, and reusability for safe, nontoxic, sustainable chemistry, and green organic synthesis, it is important to develop metalloenzyme-inspired polymer-supported metal catalysts. Here, we present a highly active, reusable, self-assembled catalyst of poly(imidazole-acrylamide) and palladium species inspired by metalloenzymes and apply our convolution methodology to the preparation of polymeric metal catalysts. Thus, a metalloenzyme-inspired polymeric imidazole Pd catalyst (MEPI-Pd) was readily prepared by the coordinative convolution of (NH4)2PdCl4 and poly[(N-vinylimidazole)-co-(N- isopropylacrylamide)5] in a methanol-water solution at 80 °C for 30 min. SEM observation revealed that MEPI-Pd has a globular-aggregated, self-assembled structure. TEM observation and XPS and EDX analyses indicated that PdCl2 and Pd(0) nanoparticles were uniformly dispersed in MEPI-Pd. MEPI-Pd was utilized for the allylic arylation/alkenylation/vinylation of allylic esters and carbonates with aryl/alkenylboronic acids, vinylboronic acid esters, and tetraaryl borates. Even 0.8-40 mol ppm Pd of MEPI-Pd efficiently promoted allylic arylation/alkenylation/vinylation in alcohol and/or water with a catalytic turnover number (TON) of 20 000-1 250 000. Furthermore, MEPI-Pd efficiently promoted the Suzuki-Miyaura reaction of a variety of inactivated aryl chlorides as well as aryl bromides and iodides in water with a TON of up to 3 570 000. MEPI-Pd was reused for the allylic arylation and Suzuki-Miyaura reaction of an aryl chloride without loss of catalytic activity.
- Yamada, Yoichi M. A.,Sarkar, Shaheen M.,Uozumi, Yasuhiro
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supporting information; experimental part
p. 3190 - 3198
(2012/04/10)
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- Facile synthesis of mono-, bis- and tris-aryl-substituted aniline derivatives in aqueous DMF
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A facile, efficient and general protocol for synthesizing a series of mono-, bis- and tris-arylsubstituted aniline derivatives is described via the Pd(OAc)2-catalyzed aerobic and ligand-free Suzuki reaction of mono-, di- and tribromoanilines with aryl boronic acids in aqueous N,Ndimethylformamide (DMF). This is the first example to prepare 2,6-bisaryl-4-nitroanilines and 2,6-bisarylanilines via a palladium-catalyzed ligand-free Suzuki reaction.
- Liu, Chun,Song, Xiaoxiao,Ni, Qijian,Qiu, Jieshan
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p. 62 - 75,14
(2020/09/02)
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- In situ generation of palladium nanoparticles: Ligand-free palladium catalyzed ultrafast Suzuki-Miyaura cross-coupling reaction in aqueous phase at room temperature
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An ultrafast and highly efficient ligand-free Suzuki-Miyaura cross-coupling reaction between aryl bromides/iodides and arylboronic acids using palladium chloride as catalyst in PEG400/H2O in air at room temperature has been developed. TEM showed that palladium nanoparticles were generated in situ from PdCl2/PEG400/H2O without use of other reductants. The catalyst system can be recycled to reuse three times with good yields.
- Du, Zhengyin,Zhou, Wanwei,Wang, Fen,Wang, Jin-Xian
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experimental part
p. 4914 - 4918
(2011/07/29)
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- Synthesis of a (piperazin-1-ylmethyl)biaryl library via microwave-mediated Suzuki-Miyaura cross-couplings
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Boc-protected (piperazin-1-ylmethyl)biaryls have been synthesised from (Boc-piperazin-1-ylmethyl)phenylboronic acid pinacol esters via a microwave-mediated Suzuki-Miyaura coupling with aryl bromides viz. 1-bromo-, 2-, 3- or 4-nitrobenzene or 2-bromo-5-nit
- Spencer, John,Baltus, Christine B.,Press, Neil J.,Harrington, Ross W.,Clegg, William
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scheme or table
p. 3963 - 3968
(2011/08/22)
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- PdO hydrate as an efficient and recyclable catalyst for the Suzuki-Miyaura reaction in water/ethanol at room temperature
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PdO?1.4H2O 1 prepared in our laboratories, as well as commercially available palladium oxides 2-4 have been found to act as efficient catalysts for the Suzuki-Miyaura reaction in ethanol/water mixture at room temperature in air. Thus, in the presence of 1 mol% catalyst, the reaction between different aryl bromides and arylboronic acids afforded a wide range of functionalized biphenyls in quantitative yield. Catalyst 1 has shown to be the most active for all couples of substrates, and it can be recovered and recycled several times without marked loss of activity. It has been demonstrated by means of suitable tests that the true catalyst is a soluble form of palladium originated by metal leaching from the metal oxide precursor. It is worth of note that the amount of catalyst both in the solution and in the isolated organic product is about 1 ppm.
- Amoroso, Francesco,Colussi, Sara,Del Zotto, Alessandro,Llorca, Jordi,Trovarelli, Alessandro
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scheme or table
p. 563 - 567
(2011/12/15)
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