- Low-cost CuNi@MIL-101 as an excellent catalyst toward cascade reaction: Integration of ammonia borane dehydrogenation with nitroarene hydrogenation
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Bimetallic CuNi nanoparticles (NPs) with low cost were rationally confined inside MIL-101 to give CuNi@MIL-101, which exhibits high efficiency and excellent recyclability toward the hydrogenation of nitroarenes under mild conditions on coupling with ammon
- Zhou, Ying-Hua,Yang, Qihao,Chen, Yu-Zhen,Jiang, Hai-Long
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Read Online
- Synergism of Pt nanoparticles and iron oxide support for chemoselective hydrogenation of nitroarenes under mild conditions
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An efficient and low-cost supported Pt catalyst for hydrogenation of niroarenes was prepared with colloid Pt precursors and α-Fe2O3 as a support. The catalyst with Pt content as low as 0.2 wt% exhibits high activities, chemoselectivi
- Jing, Pei,Gan, Tao,Qi, Hui,Zheng, Bin,Chu, Xuefeng,Yu, Guiyang,Yan, Wenfu,Zou, Yongcun,Zhang, Wenxiang,Liu, Gang
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Read Online
- NaI/PPh3-Mediated Photochemical Reduction and Amination of Nitroarenes
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A mild transition-metal- and photosensitizer-free photoredox system based on the combination of NaI and PPh3 was found to enable highly selective reduction of nitroarenes. This protocol tolerates a broad range of reducible functional groups such as halogen (Cl, Br, and even I), aldehyde, ketone, carboxyl, and cyano. Moreover, the photoredox catalysis with NaI and stoichiometric PPh3 provides also an alternative entry to Cadogan-type reductive amination when o-nitrobiarenes were used.
- Qu, Zhonghua,Chen, Xing,Zhong, Shuai,Deng, Guo-Jun,Huang, Huawen
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supporting information
p. 5349 - 5353
(2021/07/21)
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- Silver nanoparticles supported on P, Se-codoped g-C3N4 nanosheet as a novel heterogeneous catalyst for reduction of nitroaromatics to their corresponding amines
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P, Se-codoped g-C3N4 (PSeCN) nanosheet was in situ prepared by facile thermal polymerization of melamine, phosphonitrilic chloride trimer, and selenium black powder as the precursors. It was found as a suitable support for the immobilization of silver nanoparticles (Ag NPs). The prepared nanocatalyst was fully characterized via standard analysis methods including EDX, ICP-OES, XRD, FT-IR, SEM, TEM, and BET. This PSeCN/Ag nanocatalyst with a higher specific surface area compared with CN, showed excellent catalytic activity towards the reduction of several nitroaromatic compounds using sodium borohydride (NaBH4) in short reaction times with high efficiency and good selectivity in water as a green solvent. Significantly, the above-mentioned nanocomposite could be reused six times without appreciable loss of its catalytic activity.
- Elhampour, Ali,Heravi, Majid M.,Nemati, Firouzeh,Piri, Mohadese
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- Mixed-metal MOFs as efficient catalysts for transfer hydrogenation of furfural, levulinic acid and other carbonyl compounds
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Crystalline, porous Fe-Ni mixed-metal metal-organic frameworks (MOFs), namely MIL-88B(Fe2Ni) and NH2-MIL-88B(Fe2Ni), were synthesized and characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, atomic absorption spectrophotometry (AAS) and nitrogen physisorption measurements. The MOFs were then employed as catalysts for transfer hydrogenation (TH) of biomass derivatives such as furfural and levulinic acid, and various other carbonyl compounds using 2-propanol as a sacrificial hydrogen donor. These heterogeneous catalysts are deemed to be environmentally benign, efficient and recyclable. NH2-MIL-88B(Fe2Ni) showcased good catalytic activity with low catalyst loading in short reaction time. The catalysts were recovered and reused several times without significant degradation in catalytic activity. A mechanism for the TH reaction was also proposed. As far as we are aware, this is the first report on the synthesis of furfuryl alcohol and γ-valerolactone (GVL) via TH reaction in just 60 min using a MOF catalyst.
- Karvembu, Ramasamy,Raja, Duraisamy Senthil,Sindhuja, Dharmalingam,Swaminathan, Srividya,Vasanthakumar, Punitharaj
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- Visible-light induced one-pot hydrogenation and amidation of nitroaromatics with carboxylic acids over 2D MXene-derived Pt/N-TiO2/Ti3C2
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Pt nanoparticles supported on N doped titanium dioxide/titanium carbide (MXene) heterojunctions were employed as photocatalysts for the tandem reactions between aromatic nitro compounds and carboxylic acids to produce amide products. The 3%Pt/N-TiO2/Ti3C2 heterojunction was prepared by in situ grew TiO2 on Ti3C2 nanosheets and then N doped TiO2 with melamine, Pt nanoparticles with 3.3 nm mean diameter well dispersed on N-TiO2/Ti3C2. 3%Pt/N-TiO2/Ti3C2 had excellent amidation activity and chemoselectivity under visible-light irradiation. The elevated catalytic performance of 3%Pt/N-TiO2/Ti3C2 was owing to the improvement in photogenerated electron and hole separation efficiency through charge short-range directional transmission caused by the intimate contact between the TiO2 and the conductive Ti3C2. This direct hydrogenation along with amidation between nitroaromatics and carboxylic acids own actual merits in the amides produce with no harmful byproducts. In situ DRIFTS spectra verified that the amidation activation with visible light irradiation at 25 °C was much faster than heating.
- Jiang, Heyan,Hu, Zujie,Gan, Chuan,Sun, Bin,Kong, Shuzhen,Bian, Fengxia
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- Rapid, chemoselective and mild oxidation protocol for alcohols and ethers with recyclable N-chloro-N-(phenylsulfonyl)benzenesulfonamide
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Chlorine is the 20th most abundant element on the earth compared to bromine, iodine, and fluorine, a sulfonimide reagent, N-chloro-N-(phenylsulfonyl)benzenesulfonamide (NCBSI) was identified as a mild and selective oxidant. Without activation, the reagent was proved to oxidize primary and secondary alcohols as well as their symmetrical and mixed ethers to corresponding aldehydes and ketones. With recoverable PS-TEMPO catalyst, selective oxidation over chlorination of primary and secondary alcohols and their ethers with electron-donating substituents was achieved. The reagent precursor of NCBSI was recovered quantitatively and can be reused for synthesizing NCBSI.
- Badani, Purav,Chaturbhuj, Ganesh,Ganwir, Prerna,Misal, Balu,Palav, Amey
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supporting information
(2021/06/03)
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- The dehydrogenative oxidation of aryl methanols using an oxygen bridged [Cu-O-Se] bimetallic catalyst
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Herein, we report a new protocol for the dehydrogenative oxidation of aryl methanols using the cheap and commercially available catalyst CuSeO3·2H2O. Oxygen-bridged [Cu-O-Se] bimetallic catalysts are not only less expensive than other catalysts used for the dehydrogenative oxidation of aryl alcohols, but they are also effective under mild conditions and at low concentrations. The title reaction proceeds with a variety of aromatic and heteroaromatic methanol examples, obtaining the corresponding carbonyls in high yields. This is the first example using an oxygen-bridged copper-based bimetallic catalyst [Cu-O-Se] for dehydrogenative benzylic oxidation. Computational DFT studies reveal simultaneous H-transfer and Cu-O bond breaking, with a transition-state barrier height of 29.3 kcal mol?1
- Choudhury, Prabhupada,Behera, Pradyota Kumar,Bisoyi, Tanmayee,Sahu, Santosh Kumar,Sahu, Rashmi Ranjan,Prusty, Smruti Ranjita,Stitgen, Abigail,Scanlon, Joseph,Kar, Manoranjan,Rout, Laxmidhar
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supporting information
p. 5775 - 5779
(2021/04/12)
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- Atomically Dispersed Co Catalyst for Efficient Hydrodeoxygenation of Lignin-Derived Species and Hydrogenation of Nitroaromatics
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Single-atom catalysts (SACs) have attracted much attention due to their outstanding catalytic performance in heterogeneous catalysis. Here, we report a template sacrificial method to fabricate an atomically dispersed Co catalyst; three kinds of silica templates with different microstructures (MCM-41, SBA-15, and FDU-12) were employed and the effect of pore structure of the templates on the dispersity of Co was investigated. The catalysts fabricated with different templates presented different Co dispersities, leading to distinguishing catalytic performance. The optimized Co1?NC-(SBA) catalyst with atomically dispersed Co displayed outstanding catalytic activity for the hydrodeoxygenation (HDO) of lignin-derived species as well as the hydrogenation of various nitroaromatics. The reaction mechanism of the HDO of vanillin was investigated by using density functional theory calculations as well.
- Du, Congcong,Gao, Shutao,Gao, Yongjun,Huang, Jianyu,Meng, Tao,Qiao, Yuqing,Shang, Ningzhao,Shen, Tongde,Wang, Chun,Wang, Haijun,Wang, Junmin,Wang, Zhi,Wu, Qiuhua,Zhang, Longkang
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p. 8672 - 8682
(2020/09/18)
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- Cobalt oxide NPs immobilized on environmentally benign biological macromolecule-derived N-doped mesoporous carbon as an efficient catalyst for hydrogenation of nitroarenes
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Highly nitrogen-doped mesoporous carbon (N-mC) material incorporated cobalt oxide nanoparticles was synthesized through simple pyrolysis of environmentally friendly chitosan-polyaniline-Co(OAc)2 precursor in one-step. The as-prepared catalyst named CoO&at;N-mC with 14.65 ?wtpercent nitrogen content was characterized by different analysis techniques. The heterogeneous catalyst exhibits outstanding catalytic activity for the reduction of a variety of nitroaromatic compounds in the presence of NaBH4 as a reducing agent in water as a green solvent at 75 ?°C. Utilization of natural biological macromolecules such as chitosan as green and cheap starting material with harmless aniline and earth-abundant cobalt salt, facile synthesis, excellent product yield, short reaction time, high chemoselectivity, sustainable and mild reaction condition, and reusability of catalyst for at least five cycles without any significant decline in the catalytic efficiency are some prominent merits of this new nanocatalyst.
- Elhampour, Ali,Nanadegani, Zahra Soleimani,Nemati, Firouzeh,Rangraz, Yalda
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- Tuning acylthiourea ligands in Ru(II) catalysts for altering the reactivity and chemoselectivity of transfer hydrogenation reactions, and synthesis of 3-isopropoxy-1H-indole through a new synthetic approach
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Ru(II)-p-cymene complexes (1–3) containing picolyl based pseudo-acylthiourea ligands (L1-L3) were synthesized and characterized. The crystallographic study confirmed the molecular structures of all the ligands (L1-L3) and complex 3. The catalytic activity of the complexes was tested mainly towards TH of carbonyl compounds and nitroarenes. The influence of steric and electronic effects of the ligands on the chemoselectivity and reactivity were reported. The catalytic activity was enhanced and chemoselectivity was switched after tuning the ligands in the catalysts, compared to their corresponding unmodified Ru(II)-p-cymene complexes. The catalysis was extended to a broad range of substrates including some challenging systems like furfural, benzoylpyridine, benzoquinone, chromanone, etc. The strategy of tuning the bifunctional ligands in the catalysts for effective and selective catalysis worked nicely. Further, the catalysis was extended to one pot synthesis of 3-isopropoxyindole from 2-nitrocinnamaldehyde, the first synthetic route similar to Baeyer Emmerling indole synthesis. All the catalytic experiments exhibited high conversion and selectivity.
- Sathishkumar, Pushpanathan N.,Prabha, Padinhattath Sachind,Bhuvanesh, Nattamai S.P.,Karvembu, Ramasamy
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- Palladium supported on metal–organic framework as a catalyst for the hydrogenation of nitroarenes under mild conditions
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Sustainable development demands an environmentally friendly and efficient method for the hydrogenation of organic molecules, including the hydrogenation of functionalized nitroarenes. In this study, a highly active and selective metal–organic framework-supported palladium catalyst was prepared for the catalytic hydrogenation of nitroarenes. High selectivity (>99%) and excellent yield (98%) of aniline were realized after 2 hours in ethanol under hydrogen (1 atm) at room temperature. The reductions were successfully carried out in the presence of a wide range of other reducible functional groups. More importantly, the catalyst was very stable without the loss of its catalytic activity after five cycles.
- Bao, Lingxiang,Fei, Teng,Li, Jiazhe,Pang, Siping,Sun, Chenghui,Yan, Zhiyuan,Yu, Zongbao
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- Atomically precise Ag nanoclusters intercalated in zirconium pyrophosphate for efficient hydrogenation of nitroaromatics
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Designing and fabricating catalysts with highly dispersed metal nanoclusters (NCs) is very crucial for achieving high activity and selectivity. In this work, all-alkynyl-protected [Ag74(C≡CPh)44](NO3)2 cluster (
- Gong, Honghui,Lin, Lina,Zhao, Xiuge,Li, Huan,Li, Difan,Xu, Zichen,Chen, Manyu,Huang, Rong,Hou, Zhenshan
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- Metal-free chemoselective reduction of nitroaromatics to anilines via hydrogen transfer strategy
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A novel protocol for chemoselective reduction of aromatic nitro compounds to aromatic amines has been established. The metal-free reduction goes through a hydrogen transfer process. Various easily reducible functional groups can be well tolerated under the optimized reaction conditions.
- Shuai, Qi,Li, Jun,Zhao, Feng,Su, Weike,Deng, Guojun
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p. 965 - 975
(2019/04/13)
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- Synergistic Effects of ppm Levels of Palladium on Natural Clinochlore for Reduction of Nitroarenes
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Augmenting the modified naturally occurring clay clinochlore with ppm amounts of palladium leads to a new and very effective reagent for the reduction of numerous aromatic nitro species. When palladium nanoparticles are supported on pyridyltriazole-modified clinochlore, iron within clinochlore acts synergistically with palladium to catalyze the reduction of a wide variety of nitroarenes at room temperature in aqueous media. Based on E-factor calculations, the catalyst system is found to be in line with green chemistry standards and can be recycled up to five times.
- Gholinejad, Mohammad,Oftadeh, Erfan,Shojafar, Mohammad,Sansano, José M.,Lipshutz, Bruce H.
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p. 4240 - 4248
(2019/09/06)
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- A new cobalt triangular prism supramolecular flask: Encapsulation of a quinhydrone cofactor for hydrogenation of nitroarenes with high selectivity and efficiency
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A new M6L3 metal-organic triangular prism host Co–L1 was synthesized that contains a sufficiently large cavity for encapsulation of a quinhydrone (QHQ) electron transporter to form charge-transfer complexes for accelerating electron delivery. Through the strong coordinating ability of the ONP chelator, a suitable redox potential was obtained for the combination of light-driven proton reduction with the selective hydrogenation of nitro groups. The experimental results showed that the regulation of redox potential is very beneficial for hydrogen production and that the introduction of QHQ accelerates electron transfer and increases the reaction rate. Control experiments based on an inhibitor and a mononuclear compound resembling the cobalt corner of the triangular prism suggest enzyme-like behaviour. This synthetic platform, in which the supramolecular systems exhibit high activity and stability, provides an alternative strategy to selectively hydrogenate nitroarenes using light as a clean energy source.
- Zheng, Sijia,Zhao, Liang,Wei, Jianwei,He, Cheng,Liu, Guangzhou,Duan, Chunying
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- Method for selectively oxidizing cumene compounds
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The invention relates to a method for selectively oxidizing cumene compounds, and the method comprises the following steps: placing cumene compounds shown in a formula (I), an iron porphyrin catalyst,an oxidant and a dispersant into a ball milling tank, sealing the ball milling tank, performing ball milling for 3 to 24 hours at a rotating speed of 100 to 800 rpm at room temperature, stopping ballmilling once every 1 to 3 hours in the ball milling process, discharging gases in the ball milling tank, finishing the reaction, and performing post-treatment on a reaction mixture to obtain product2-phenyl-2-propanol compound shown in a formula (II); according to the invention, the oxidation conversion of the cumene and derivatives thereof is realized through solid-phase ball milling, the reaction mode is novel, the operation is convenient, and the energy consumption is low; the method needs no organic solvent, thus effectively avoiding the use of toxic and harmful organic solvents and being green and environment-friendly; has low peroxide content and high safety factor, and high 2-phenyl-2-propanol and derivative selectivity and meets the social requirements of the current green chemical process, environmental compatibility chemical process and biological compatibility chemical process.
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Paragraph 0117; 0118
(2019/11/21)
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- The synthesis of methyl triazole-4-carboxylate gold(I) complex and application on allene synthesis and alkyne hydration
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The methyl 1H-1,2,3-triazole-4-carboxylate containing a strong electron-withdrawing group was developed and applied as a ligand for gold(I) cations. The resulting ester-triazole gold(I) complex was investigated for its efficiency in catalyzing allene synthesis and alkyne hydration, in which an excellent catalytic efficiency was observed with low catalyst loadings.
- Hu, Wenkang,Shan, Liang,Ma, Fudong,Zhang, Yilin,Yang, Yongchun,Wang, Dawei
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- Mechanochemical catalytic transfer hydrogenation of aromatic nitro derivatives
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Mechanochemical ball milling catalytic transfer hydrogenation (CTH) of aromatic nitro compounds using readily available and cheap ammonium formate as the hydrogen source is demonstrated as a simple, facile and clean approach for the synthesis of substituted anilines and selected pharmaceutically relevant compounds. The scope of mechanochemical CTH is broad, as the reduction conditions tolerate various functionalities, for example nitro, amino, hydroxy, carbonyl, amide, urea, amino acid and heterocyclic. The presented methodology was also successfully integrated with other types of chemical reactions previously carried out mechanochemically, such as amide bond formation by coupling amines with acyl chlorides or anhydrides and click-type coupling reactions between amines and iso(thio)cyanates. In this way, we showed that active pharmaceutical ingredients Procainamide and Paracetamol could be synthesized from the respective nitro-precursors on milligram and gram scale in excellent isolated yields.
- Portada, Tomislav,Margeti?, Davor,?trukil, Vjekoslav
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supporting information
(2018/12/11)
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- Simple and Practical Synthesis of Various New Nickel Boride-Based Nanocomposites and their Applications for the Green and Expeditious Reduction of Nitroarenes to Arylamines under Wet-Solvent-Free Mechanochemical Grinding
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In this paper, we report a simple synthesis of four new nickel boride-based nanocomposites, namely Ni2B@ZrCl4, Ni2B@Cu2O, Ni2B@CuCl2 and Ni2B@FeCl3, from commercially available and cheap starting materials. All of the new Ni2B-based nanocomposites were well characterized by Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. Further, the catalytic applications of these new nanocomposites were successfully evaluated in the wet-solvent-free reduction of aromatic nitro compounds to arylamines with sodium borohydride (NaBH4) at room temperature by a mechanochemical grinding technique. All the introduced catalytic systems provide excellent yields of arylamines in very short reaction times for a wide range of substrates. Also, recoverability and reusability of the new nanocomposites were investigated.
- Mousavi, Hossein,Zeynizadeh, Behzad,Younesi, Reza,Esmati, Mozhgan
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p. 595 - 609
(2018/09/10)
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- Tariquidar-Related Chalcones and Ketones as ABCG2 Modulators
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ABC transporters, including ABCG2, play a vital role in defending the human body against the vast range of xenobiotics. Even though this is beneficial for human health, these protein transporters have been implicated in the emerging resistance of cancer c
- Pe?a-Solórzano, Diana,Scholler, Matthias,Bernhardt, Günther,Buschauer, Armin,K?nig, Burkhard,Ochoa-Puentes, Cristian
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supporting information
p. 854 - 859
(2018/08/03)
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- Nitro group reduction and Suzuki reaction catalysed by palladium supported on magnetic nanoparticles modified with carbon quantum dots generated from glycerol and urea
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Glycerol and urea were used as green and cheap sources of carbon quantum dots (CQD) for modifying Fe3O4 nanoparticles (NPs). The obtained CQD@Fe3O4 NPs were used for the stabilization of palladium species and the prepared catalyst, Pd@CQD@Fe3O4, was characterized using various techniques. This magnetic supported palladium was applied as an efficient catalyst for the reduction of aromatic nitro compounds to primary amines at room temperature using very low palladium loading (0.008?mol%) and also for the Suzuki–Miyaura cross-coupling reaction of aryl halides as well as challenging heteroaryl bromides and aryl diazonium salts with arylboronic acids and with potassium phenyltrifluoroborate. This magnetically recyclable catalyst was recovered and reused for seven consecutive runs in the reduction of 4-nitrotoluene to p-toluidine and for ten consecutive runs in the reaction of 4-iodoanisole with phenylboronic acid with small decrease of activity. The catalyst reused in the Suzuki reaction was characterized using transmission electron microscopy, vibrating sample magnetometry and X-ray photoelectron spectroscopy. Using experiments such as hot filtration and poisoning tests, it has been shown that the true catalyst works under homogeneous conditions according to the release–return pathway of active palladium species.
- Gholinejad, Mohammad,Zareh, Fatemeh,Nájera, Carmen
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- Pd supported on g-C3N4 nanosheets: Mott-Schottky heterojunction catalyst for transfer hydrogenation of nitroarenes using formic acid as hydrogen source
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Well-dispersed Pd nanoparticles were anchored on g-C3N4 nanosheets, which were prepared by a liquid-phase exfoliation method. The hybrid material displayed excellent catalytic activity for the transfer hydrogenation of nitroarenes. The reactions can be conducted smoothly in water at room temperature with formic acid as hydrogen source. Aniline was produced in excellent yield (>99%; turnover frequency: 853), surpassing the majority of reported heterogeneous catalysts using formic acid or formates as hydrogen source. The increased activity of such a hybrid catalyst can be ascribed to the nitrogen-rich and amphipathic property of the carbon nitride support, the stable and uniform dispersed Pd nanoparticles and the Mott-Schottky effect between the g-C3N4 nanosheets and the metal nanoparticles. The heterogeneous Mott-Schottky catalyst can be reused for five cycles without any obvious loss of its catalytic activity.
- Cheng, Saisai,Meng, Xufeng,Shang, Ningzhao,Gao, Shutao,Feng, Cheng,Wang, Chun,Wang, Zhi
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p. 1771 - 1778
(2018/02/09)
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- Nitrogen-Doped Graphene-Supported Iron Catalyst for Highly Chemoselective Hydrogenation of Nitroarenes
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A nitrogen-doped graphene-supported iron catalyst was used for the first time in the hydrogenation of a series of nitroarenes to give the corresponding amines with excellent activity and chemoselectivity under mild reaction conditions. Physicochemical characterization of the catalyst by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and M?ssbauer spectroscopy revealed the formation of iron particles with an iron oxide core and a metallic iron shell that were coated by a few layers of nitrogen-doped graphene. The unique structure of FeNx/C in the catalyst was proven to contribute to the hydrogenation activity.
- Wei, Zuojun,Hou, Yaxin,Zhu, Xinmiao,Guo, Liangyu,Liu, Yingxin,Zhang, Anyun
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p. 2009 - 2013
(2018/03/21)
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- Pd nanoparticles supported on a covalent triazine-based framework material: An efficient and highly chemoselective catalyst for the reduction of nitroarenes
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Pd nanoparticles anchored on a covalent triazine framework (Pd@CTF) were fabricated and employed to catalyze the transfer hydrogenation of nitro-compounds with formic acid as the hydrogen source. The results demonstrated that Pd@CTF displayed excellent catalytic activity and high chemoselectivity for the hydrogenation reaction at room temperature. Various substituted nitro-compounds were successfully converted to the corresponding amines in 0.2-2.5 h with other reducible functional moieties remaining intact. The high performance of Pd@CTF can be attributed to the synergistic interaction between the highly dispersed Pd nanoparticles and the covalent triazine framework support. The Pd@CTF catalyst can be readily reused for at least five consecutive runs without an obvious loss of its catalytic activity.
- Li, Jie,Zhang, Lihong,Liu, Xiaotong,Shang, Ningzhao,Gao, Shutao,Feng, Cheng,Wang, Chun,Wang, Zhi
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p. 9684 - 9689
(2018/06/18)
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- Preparation and characterization of Fe3O4/SiO2/CdS nanocomposites as efficient magnetic photocatalysts for the reduction of nitro compounds under visible LED irradiation
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A series of magnetic Fe3O4/SiO2/CdS nanocomposites were synthesized through a facile and convenient method. The characterization of the prepared nanocomposites was performed by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), vibrating sample magnetometer (VSM), UV–Vis spectroscopy, and UV–vis diffuse reflectance spectroscopy (DRS). The prepared magnetic photocatalysts were first utilized for the photocatalytic reduction of nitro compounds under visible LED irradiation. The Fe3O4/SiO2/CdS nanocomposites exhibited enhanced photoactivity compared with the bare CdS and commercial CdS (Aldrich). The results demonstrated that Fe3O4/SiO2/CdS nanocomposites have potential to provide a promising visible light driven photocatalyst for the selective reduction of nitro compounds to corresponding amines under mild conditions. The prepared photocatalyst can be recovered by magnetic separation and successfully reused for 3 cycles.
- Eskandari, Parvin,Kazemi, Foad
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p. 233 - 239
(2018/06/15)
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- Chemoselective transfer hydrogenation of nitroarenes, ketones and aldehydes using acylthiourea based Ru(II)(p-cymene) complexes as precatalysts
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A new series of Ru(II)(η6-p-cymene) complexes (1–5) was synthesized from pyridine based acylthiourea ligands (L1-L5) and [Ru(η6-p-cymene)Cl2]2. All the ligands and complexes were well characterized by UV-Visible, FT-IR, mass and 1H & 13C NMR spectroscopic techniques. The molecular structures of the ligands (L1, L2, L4 and L5) and complex 1 were confirmed using single crystal X-ray diffraction study. The Ru(II)(η6-p-cymene) complexes (1–5) were proved to be efficient precatalysts for the transfer hydrogenation of carbonyl compounds and nitroarenes in the presence of 2-propanol as a hydrogen donor and KOH as a base. The catalytic transfer hydrogenation reactions were chemoselective towards the nitro group in presence of carbonyl group, which is a rare scenario in homogeneous catalysis. The catalyst was compatible with broad range of substrates which include furfural, quinone and many heterocycles. The catalytic reactions exhibited very high conversions (upto 100%) and excellent yields (upto 99%). Turn Over Number (TON) was found upto 990.
- Sathishkumar, Pushpanathan N.,Raveendran, Neethi,Bhuvanesh, Nattamai S.P.,Karvembu, Ramasamy
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- Highly Efficient Pt-Catalyst Supported on Mesoporous Ceria-Zirconia Oxide for Hydrogenation of Nitroaromatic Compounds to Anilines
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Abstract: In this work, we have prepared a new catalytic system based on highly dispersed Pt nanoparticles supported on mesoporous ceria-zirconia oxide. The unique ability of the synthesized catalyst to activate hydrogen in the temperature range from –50 to 25°C allows us to provide selective hydrogenation of nitro-aromatic compounds to anilines at room temperature and atmospheric pressure of H2.
- Redina,Vikanova
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p. 2374 - 2378
(2019/01/03)
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- Metal/catalyst/reagent free hydration of alkynes up to gram scale under temperature and pressure controlled condition
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A new green water-mediated metal/catalyst/reagent-free methodology for hydration of alkyne is devised. The remarkable yields of various ketones were achieved when alkynes were heated at 150 °C under 11 bar pressure in an autoclave for 14 h in water-methanol solution. Outstanding functional group compatibility for both the terminal and internal alkynes was established. This methodology produces excellent yields up to gram scale under optimised reaction condition.
- Ali, Munsaf,Srivastava, Avinash K.,Joshi, Raj K.
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p. 2075 - 2078
(2018/05/04)
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- Photo induced alkyne hydration reactions mediated by a water soluble, reusable Rhodium (I) catalyst
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Under photochemical irradiation, the hydration of aryl alkynes in the presence of water proceeds in good yields to afford the corresponding ketone, using a water-soluble rhodium (I) catalyst. The catalyst is effective for internal and terminal alkynes and showed high functional group compatibility. A low catalyst loading, low temperature and shorter duration of photolysis are ideal feature of reaction. The catalyst can be reused several times under aerobic and aqueous conditions, exemplifying the robust nature of the catalyst. In comparison with known Rh and other metal catalysts, the present reaction provides a remarkable green approach for alkyne hydration reactions.
- Ali, Munsaf,Srivastava, Avinash K.,Siangwata, Shepherd,Smith, Gregory S.,Joshi, Raj K.
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- Amphiphilic Zwitterionic phosphine based Au(I)-complex as efficient and recyclable catalyst for hydration of alkynes free of additional additives
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The unique amphiphilic Zwitterionic P,O-hybrid ligand (L1) containing phosphino-fragment and ?SO3? group was synthesized and firstly applied in Au-catalyzed hydration of alkynes. Without the aid of any auxiliary additive such as acid or silver salt, L1-based Au-catalyst exhibited excellent activity towards hydration of alkynes to yield ketones with 100% selectivity according to Markovnikov's rule. On the other hand, L1-based Au-catalyst could be recycled for 4 runs in room temperature ionic liquid of [Bmim]PF6 without obvious activity loss, and also exhibited wide generality to the hydration of different alkynes.
- Chen, Xia,Ye, Xu,Liang, Wen-Yu,Zhou, Qing,Vo-Thanh, Giang,Liu, Ye
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p. 171 - 176
(2018/03/01)
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- A photocatalytic green system for chemoselective reduction of nitroarenes
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A highly efficient photocatalytic reduction of nitroarenes using TiO2/polyethylene glycol 400-water (TiO2/PEG-H2O) is reported. This system at deoxygenated and illuminated (sunlight or violet LED) conditions efficiently reduced nitroarenes using oxalic acid or ammonium formate as a sacrificial electron donor. Reducible functional groups such as chloro, hydroxy, flouro, bromo and carbonyl were intact under the optimized reaction conditions. The 0.1 and 0.5-1 mmol amount of nitroarenes was used under sunlight and violet LED (400 nm) irradiation, respectively. Reusability of the nanotitania was successfully carried out four times. The analyses of the recovered catalyst after five runs including TEM, XRD, TGA and CHN were done and results showed that PEG is located on TiO2; no change in morphology, crystallinity and particle sizes was observed.
- Ramdar, Moosa,Kazemi, Foad,Kaboudin, Babak
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p. 1155 - 1163
(2017/05/17)
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- ZnAl-Hydrotalcite-Supported Au25Nanoclusters as Precatalysts for Chemoselective Hydrogenation of 3-Nitrostyrene
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Chemoselective hydrogenation of 3-nitrostyrene to 3-vinylaniline is quite challenging because of competitive activation of the vinyl group and the nitro group over most supported precious-metal catalysts. A precatalyst comprised of thiolated Au25nanoclusters supported on ZnAl-hydrotalcite yielded gold catalysts of a well-controlled size (ca. 2.0 nm)—even after calcination at 500 °C. The catalyst showed excellent selectivity (>98 %) with respect to 3-vinylaniline, and complete conversion of 3-nitrostyrene over broad reaction duration and temperature windows. This result is unprecedented for gold catalysts. In contrast to traditional catalysts, the gold catalyst is inert with respect to the vinyl group and is only active with regard to the nitro group, as demonstrated by the results of the control experiments and attenuated total reflection infrared spectra. The findings may extend to design of gold catalysts with excellent chemoselectivity for use in the synthesis of fine chemicals.
- Tan, Yuan,Liu, Xiao Yan,Zhang, Leilei,Wang, Aiqin,Li, Lin,Pan, Xiaoli,Miao, Shu,Haruta, Masatake,Wei, Haisheng,Wang, Hua,Wang, Fangjun,Wang, Xiaodong,Zhang, Tao
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supporting information
p. 2709 - 2713
(2017/02/26)
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- A 4, 4 - dimethoxy - 2, 2 - bipyridyl silver catalytic hydrogenation of aromatic nitro compound synthesis of aromatic amines (by machine translation)
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The invention discloses a 4, 4 - dimethoxy - 2, 2 - bipyridyl silver catalytic hydrogenation of aromatic nitro compound synthesis of aromatic amines, the method uses a cheap, easy synthesis of 4, 4 - dimethoxy - 2, 2 - bipyridyl silver as catalyst, in order to green, environmental protection, non-toxic as the hydrogen source, the aromatic nitro compound in the relatively mild reaction conditions, one-step reaction can synthesize aromatic amine. The invention has simple operation, catalyst is cheap and easy and small consumption, mild reaction conditions, to substrate demonstrates better functional group tolerant, high product yield, industrial manufacturing cost, it has very good application prospect. (by machine translation)
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Paragraph 0013; 0016
(2017/07/19)
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- Magnetically nano core–shell Fe3O4@Cu(OH)x: a highly efficient and reusable catalyst for rapid and green reduction of nitro compounds
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Magnetically separable nano core–shell Fe3O4@Cu(OH)x with 22?% Cu content was prepared by the addition of sodium hydroxide to a mixture of CuCl2·2H2O and nano Fe3O4 in water. Characterization of the impregnated copper hydroxide was carried out by X-ray fluorescence (XRF), X-ray diffraction (XRD) atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM), value stream mapping (VSM) and Brunauer–Emmett–Teller (BET) analysis. The core–shell nanocatalyst exhibited the excellent catalytic activity toward reduction of various nitro compounds to the corresponding amines with NaBH4. All reactions were carried out in H2O (55–60?°C) within 3–15?min to afford amines in high to excellent yields. Reusability of core–shell Cu(OH)x catalyst was examined 9?times without significant loss of its catalytic activity.
- Shokri, Zahra,Zeynizadeh, Behzad,Hosseini, Seyed Ali,Azizi, Behrooz
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p. 101 - 109
(2017/01/05)
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- Palladium on Polydopamine: Its True Potential in Catalytic Transfer Hydrogenations and Heck Coupling Reactions
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The application of Pd–polydopamine and magnetic Fe3O4@Pd–polydopamine catalysts in catalytic transfer hydrogenation reactions and the Heck arylation is reported. The reduction of a wide range of aromatic nitro-compounds bearing both electron-donating and -withdrawing substituents to the corresponding anilines could be efficiently performed, although the reduction of carbonyl compounds was found to be less general. In the latter case, only aromatic ketones could be reduced to the corresponding alcohols, whereas aldehyde substrates were unaffected, which may be owing to their reaction with the catalyst support leading to catalyst deactivation. By using magnetic Fe3O4@Pd–polydopamine system, facilitated catalyst recovery and reuse for five consecutive cycles without considerable loss of activity in nitro-group reduction. The efficiency of the catalyst in Heck reactions was comparable to that in transfer hydrogenation, however, no catalytic activity was observed upon reuse in this case, likely as a result of metal leaching. We also explored tandem Heck reaction/catalytic transfer hydrogenation sequences, however, the two reactions showed limited compatibility under the applied conditions.
- Kunfi, Attila,Szabó, Vivien,Mastalir, ágnes,Bucsi, Imre,Mohai, Miklós,Németh, Péter,Bertóti, Imre,London, Gábor
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supporting information
p. 3236 - 3244
(2017/08/29)
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- Photoinduced Reduction of Nitrobenzenes to Primary Aromatic Amines
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Primary aromatic amines were synthesized from the corresponding nitrobenzenes via photoinduced reduction. The reaction was found to be effective when nitrobenzenes with electron-withdrawing substituents were irradiated with a broad band of UV light centered at 306 nm. When reactions are completed, products could be isolated by acid-base extraction or by column chromatography. This presenting photoreaction procedure for the synthesis of primary aromatic amines from the corresponding nitrobenzenes proceeds without the need of a sensitizer in isopropanol or THF. Without the usage of catalysts, or stoichiometric reducing reagent containing heavy metals, this photoinduced reduction of nitrobenzenes fulfils the concept of green chemistry.
- Huang, Hua-Hsuan,Chen, Yu-Feng,Niu, Guang-Hao,Chuang, Gary J.
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supporting information
p. 1191 - 1194
(2017/06/13)
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- High catalytic activity of a bimetallic AgPd alloy supported on UiO-66 derived porous carbon for transfer hydrogenation of nitroarenes using formic acid-formate as the hydrogen source
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Bimetallic AgPd nanoparticles anchored on metal-organic framework (UiO-66) derived N-doped porous carbon (NPC-UiO-66) was fabricated and used as a catalyst for the catalytic transfer hydrogenation of nitroarenes using formic acid-formate as the hydrogen source. The results demonstrated that the Ag1Pd9@NPC-UiO-66 composite exhibited extraordinary catalytic activity toward the hydrogenation of nitroarenes to anilines at room temperature. A series of substituted nitroarenes were successfully converted to the corresponding anilines in high yields under ambient conditions with other reducible groups remaining intact. The superior catalytic performance of the prepared catalyst can be attributed to the synergistic effect between the highly dispersed AgPd nanoparticles and the unique structure of the NPC-UiO-66 support, as well as the high adsorption ability of the catalyst for the nitroarenes.
- Cheng, Saisai,Shang, Ningzhao,Zhou, Xin,Feng, Cheng,Gao, Shutao,Wang, Chun,Wang, Zhi
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p. 9857 - 9865
(2017/09/18)
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- Co-based heterogeneous catalysts from well-defined Α-diimine complexes: Discussing the role of nitrogen
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Ar-BIANs and related α-diimine Co complexes were wet impregnated onto Vulcan XC 72 R carbon black powder and used as precursors for the synthesis of heterogeneous supported nanoscale catalysts by pyrolysis under argon at 800?°C. The catalytic materials feature a core-shell structure composed of metallic Co and Co oxides decorated with nitrogen-doped graphitic layers (NGr). These catalysts display high activity in the liquid phase hydrogenation of aromatic nitro compounds (110?°C, 50 bar H2) to give chemoselectively substituted aryl amines. The catalytic activity is closely related to the amount and type of nitrogen atoms in the final catalytic material, which suggests a heterolytic activation of dihydrogen.
- Formenti, Dario,Ferretti, Francesco,Topf, Christoph,Surkus, Annette-Enrica,Pohl, Marga-Martina,Radnik, J?rg,Schneider, Matthias,Junge, Kathrin,Beller, Matthias,Ragaini, Fabio
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- A highly efficient heterogeneous copper-catalysed cascade reaction of aryl iodides with acetamidine hydrochloride leading to primary arylamines
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A highly efficient heterogeneous copper-catalysed cascade reaction of aryl iodides with acetamidine hydrochloride was achieved in DMF in the presence of 10 mol% of an MCM-41-immobilised L-proline-copper(I) complex (MCM-41-L-proline-CuI) with Cs2CO3 as base, yielding a variety of primary arylamines in good to excellent yields. The new heterogeneous copper complex can be easily prepared from commercially readily available and inexpensive reagents, recovered by a simple filtration of the reaction solution and used at least seven more times without any decrease in activity.
- Huang, Xue,Xiao, Ruian,You, Chongren,Yan, Tao,Cai, Mingzhong
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p. 315 - 320
(2017/06/19)
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- Discovery of N-(Naphthalen-1-yl)-N′-alkyl Oxalamide Ligands Enables Cu-Catalyzed Aryl Amination with High Turnovers
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A class of N-(naphthalen-1-yl)-N′-alkyl oxalamides have been proven to be powerful ligands, making a coupling reaction of (hetero)aryl iodides with primary amines proceed at 50 °C with only 0.01 mol % of Cu2O and ligand as well as a coupling reaction of (hetero)aryl bromides with primary amines and ammonia at 80 °C with only 0.1 mol % of Cu2O and ligand. A wide range of coupling partners work well under these conditions, thereby providing an easy to operate method for preparing (hetero)aryl amines.
- Gao, Jie,Bhunia, Subhajit,Wang, Kailiang,Gan, Lu,Xia, Shanghua,Ma, Dawei
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supporting information
p. 2809 - 2812
(2017/06/07)
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- Visible light active CdS nanorods: One-pot synthesis of aldonitrones
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This is the first report on nano semiconductor photocatalytic synthesis of aldonitrones through in situ trapping of hydroxylamine intermediates in the presence of aromatic aldehydes in aqueous media under visible light irradiation. A new highly efficient dispersible CdS nanorod photocatalyst was synthesized. The characterization of the catalyst was done by transmission electron microscopy (TEM), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) analysis, CHNS elemental analysis, thermogravimetric analysis (TGA) and diffuse reflection spectroscopy (DRS). The CdS nanorods have 12-18 nm sizes according to TEM. The catalyst was used successfully in the chemoselective photocatalytic reduction of nitroarenes using a CdS/poly ethyleneglycol 400-water system (CdS/PEG-H2O). The reaction was successfully carried out under green and blue LED illumination by using ammonium formate as a sacrificial electron donor in the presence and absence of an aldehyde, producing aromatic amines or aromatic nitrones respectively. The reusability of the CdS nanorod photocatalyst was tested four times. Moreover, the stability of the catalyst was confirmed by the characterization of a reused catalyst.
- Ramdar, Moosa,Kazemi, Foad,Kaboudin, Babak,Taran, Zahra,Partovi, Adel
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p. 9257 - 9262
(2016/11/09)
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- Method for catalytic reduction of m-nitroacetophenone for preparation of m-aminoacetophenone
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The present invention provides a method for catalytic reduction of m-nitroacetophenone for preparation of m-aminoacetophenone, according to the method, hydrogen is used as a reducing agent, bismuth-compound-supported Pt is used as a catalyst, and the m-ni
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Paragraph 0015; 0016
(2016/10/27)
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- Stable and reusable platinum nanocatalyst: An efficient chemoselective reduction of nitroarenes in water
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Binaphthyl stabilized Pt nanoparticles (Pt-BNP) have been synthesized, characterized, and utilized as an efficient heterogeneous catalyst for chemoselective reduction of nitroarenes at room temperature in water. Several sensitive functional groups like ketone, ester, acid, amide, halides, and nitrile were well tolerated in this chemoselective reduction. The Pt-BNP catalyst was quantitatively recovered without any major change in particle size and reactivity and then efficiently reused for five catalytic cycles.
- Kotha, Surya Srinivas,Sharma, Nidhi,Sekar, Govindasamy
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supporting information
p. 1410 - 1413
(2016/03/12)
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- Preparation method of 2-bromo-3'-methoxyacotophenone
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The invention relates to a preparation method of a medical intermediate, in particular to a preparation method of 2-bromo-3'-methoxyacotophenone. According to the preparation method, the target product is prepared by taking acetophenone, dimethyl sulfate and a brominating agent as main raw materials through the steps of a nitration reaction, a reduction reaction, a diazotization reaction, a hydrolysis reaction, a methylation reaction, a bromination reaction and the like. The preparation method has the advantages that the yields of the reactions are all 80% or above, the purity of the obtained target product 2-bromo-3'-methoxyacotophenone can reach 99.2%, the cost is low, and the yield and the purity are high; in the preparation process, the reaction conditions are mild, operation is easy, little harm is generated to the environment, and the preparation method is suitable for large-scale production.
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Paragraph 0029; 0036; 0043
(2017/08/25)
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- Base-Free Transfer Hydrogenation of Nitroarenes Catalyzed by Micro-Mesoporous Iron Oxide
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An efficient and practical protocol for the transfer hydrogenation of nitroarenes was developed, which uses flower-shaped micro-mesoporous iron oxide (MMIO) with formic acid as the reducing agent and tris[(2-diphenylphosphino)-ethyl]phosphine as the ligand in the absence of an additional base. The recyclable catalytic system enables the reduction of the nitro group in a broad range of substrates to yield valuable amines and shows a high tolerance to sensitive functional groups.
- Datta, Kasibhatta J.,Rathi, Anuj K.,Gawande, Manoj B.,Ranc, Vaclav,Zoppellaro, Giorgio,Varma, Rajender S.,Zboril, Radek
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p. 2351 - 2355
(2016/07/28)
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- Using the hydrogen and oxygen in water directly for hydrogenation reactions and glucose oxidation by photocatalysis
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Direct utilization of the abundant hydrogen and oxygen in water for organic reactions is very attractive and challenging in chemistry. Herein, we report the first work on the utilization of the hydrogen in water for the hydrogenation of various organic compounds to form valuable chemicals and the oxygen for the oxidation of glucose, simultaneously by photocatalysis. It was discovered that various unsaturated compounds could be efficiently hydrogenated with high conversion and selectivity by the hydrogen from water splitting and glucose reforming over Pd/TiO2 under UV irradiation (350 nm). At the same time, glucose was oxidated by the hydroxyl radicals from water splitting and the holes caused by UV irradiation to form biomass-derived chemicals, such as arabinose, erythrose, formic acid, and hydroxyacetic acid. Thus, the hydrogen and oxygen were used ideally. This work presents a new and sustainable strategy for hydrogenation and biomass conversion by using the hydrogen and oxygen in water.
- Zhou, Baowen,Song, Jinliang,Zhou, Huacong,Wu, Tianbin,Han, Buxing
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p. 463 - 468
(2015/12/26)
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- Synthesis of Nickel Nanoparticles with N-Doped Graphene Shells for Catalytic Reduction Reactions
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The synthesis of novel nanoparticles is of general importance for the development of efficient heterogeneous catalysts. Herein, the preparation of carbon-supported nickel-based nanoparticles (NPs), modified by nitrogen-doped graphene layers, is reported for the first time. The resulting materials were characterized in detail by TEM, X-ray photoelectron spectroscopy (XPS), XRD, elemental analysis (EA), electron paramagnetic resonance (EPR), temperature-programmed reduction (TPR), BET, and Raman analysis. Initial catalytic tests revealed the potential of this class of compounds in hydrogenation reactions.
- Pisiewicz, Sabine,Formenti, Dario,Surkus, Annette-Enrica,Pohl, Marga-Martina,Radnik, J?rg,Junge, Kathrin,Topf, Christoph,Bachmann, Stephan,Scalone, Michelangelo,Beller, Matthias
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p. 129 - 134
(2016/01/25)
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- One-pot synthesis of 1,4-disubstituted 1,2,3-triazoles from nitrobenzenes
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A facile synthesis of 1,4-disubstituted 1,2,3-triazoles was achieved from nitrobenzenes and terminal alkynes under mild conditions. The reactions were successful for nitrobenzenes and terminal alkynes bearing various functionalities, from which the 1,2,3-triazole derivatives were smoothly synthesized through a four-step one-pot sequence.
- Zhao, Fen,Chen, Zhen,Xie, Kai,Yang, Rui,Jiang, Yu-Bo
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p. 109 - 113
(2016/01/25)
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- Photocatalytic reduction of nitro aromatic compounds to amines using a nanosized highly active CdS photocatalyst under sunlight and blue LED irradiation
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A variety of aromatic nitro compounds were chemoselectively reduced to the corresponding anilines using conveniently prepared nanosized CdS as a photocatalyst under the sunlight and blue LED irradiation. The results demonstrated that synthesized CdS nanostructures have the potential to provide a promising visible light driven photocatalyst for chemoselective reduction of nitro aromatics in the presence of nitrile and carbonyl groups to the corresponding amines under both sunlight and blue LED irradiation. Photoreduction of nitro aromatics by the prepared nanosized CdS with high surface area was faster than when using the commercially available CdS under both sunlight and LED irradiation. Nanosized CdS photocatalyst was prepared by a simple method without any capping agent. X-ray diffraction (XRD), energy dispersive spectrometry (EDAX), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2 absorption-desorption, diffuse reflectance spectroscopy (DRS), and flat band potential methods were employed for the characterization, which revealed that the prepared CdS nanoparticles have a well-resolved cubic structure with the size of around 10-30 nm and a band gap of 2.37 eV.
- Asghar Safari, Ali,Kazemi, Foad
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p. 531 - 537
(2016/03/08)
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