- Design, synthesis and evaluation of novel tacrine-multialkoxybenzene hybrids as multi-targeted compounds against Alzheimer's disease
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A series of benzoates (or phenylacetates or cinnamates) - tacrine hybrids (7a-o) were designed, synthesized and evaluated as multi-potent anti-Alzheimer drug candidates. The screening results showed that most of them exhibited a significant ability to inhibit ChEs, certain selectivity for AChE over BuChE and strong potency inhibitory of self-induced β-amyloid (Aβ) aggregation. All IC50 values of biological activity were at the nanomolar range. Especially, compound 7c displayed the greatest ability to inhibit AChE with an IC50 value of 5.63 nM and the highest selectivity with ratio of BuChE/AChE value of 64.6. Moreover, it also exhibited a potent inhibitory of Aβ aggregation with an IC50 value of 51.81 nM. A Lineweaver-Burk plot and molecular modeling study showed that compound 7c targeted both the CAS and PAS of ChEs. A structure-activity relationship analysis suggested that the electron density of aromatic ring which was linked with tacrine through acetyl group played a significant role in determining the inhibitory activity.
- Zhang, Chao,Du, Qiao-Yi,Chen, Lang-Di,Wu, Wen-Hao,Liao, Si-Yan,Yu, Li-Hong,Liang, Xin-Tong
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Read Online
- Design, synthesis and evaluation of novel hybrids between 4-anilinoquinazolines and substituted triazoles as potent cytotoxic agents
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In this research several series of novel dioxygenated ring fused 4-anilinoquinazolines (10a-d) and 4-anilinoquinazoline-substituted triazole hybrid compounds (11–14) have been designed and synthesized. Their biological significance was highlighted by evaluating in vitro for anticancer activities, wherein several compounds displayed excellent activity specifically against three human cancer cell lines (KB, epidermoid carcinoma; HepG2, hepatoma carcinoma; SK-Lu-1, non-small lung cancer). Especially, compound 13a exhibited up to 100-fold higher cytotoxicity in comparison with erlotinib. Docking the most cytotoxic compounds (11d, 13a, 13b, and 14c) into the ATP binding site of different EGFR tyrosine kinase domains was perfomed to predict the analogous binding mode of these compounds to the EGFR targets.
- Le-Nhat-Thuy, Giang,Dinh, Thuy Van,Pham-The, Hai,Nguyen Quang, Hung,Nguyen Thi, Nga,Dang Thi, Tuyet Anh,Hoang Thi, Phuong,Le Thi, Tu Anh,Nguyen, Ha Thanh,Nguyen Thanh, Phuong,Le Duc, Trung,Nguyen, Tuyen Van
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Read Online
- Ring-expansion reaction of cyano-substituted singlet phenyl nitrenes: Theoretical predictions and kinetic results from laser flash photolysis and chemical trapping experiments
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On the basis of the open-shell electronic structure of the lowest-singlet state of phenylnitrene, it is predicted that substitution of a radical-stabilizing cyano group at an ortho carbon should facilitate cyclization at that carbon, whereas cyano substitution at the para carbon should retard the rate of cyclization. These qualitative predictions have been tested computationally by performing (8/8)CASSCF and CASPT2/6-31G* ab initio calculations and experimentally by carrying out laser flash photolysis and chemical trapping studies. The calculations and experiments both find that, unlike the case with ortho fluoro and ortho methyl substituents, the rate of cyclization at a substituted carbon is not retarded by an ortho cyano group. In contrast, a para cyano group is found, both computationally and experimentally, to raise the barrier to cyclization of singlet phenylnitrene by > 1 kcal/mol.
- Gritsan,Likhotvorik,Tsao,Celebi,Platz,Karney,Kemnitz,Borden
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Read Online
- 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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- Transformations of 2-Ethyl-2-methyl-2,3-dihydro-1H-indole at the 3-Position
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The oxidation of N-acetyl-2-ethyl-2-methyl-2,3-dihydro-1H-indole with pyridinium chlorochromate, CrO3 · 2 Py, or CrO3 gave N-acetyl-2-ethyl-2-methyl-2,3-dihydro-1H-indol-3-one which was hydrolyzed to 2-ethyl-2-methyl-2,3-dihydro-1H-i
- Abdrakhmanov, I. B.,Latypova, L. R.,Mustafin, A. G.,Salikhov, Sh. M.
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Read Online
- Cu(OAc)2 catalysed aerobic oxidation of aldehydes to nitriles under ligand-free conditions
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An economically efficient and environmentally benign approach for the direct oxidative transformation of aldehydes to nitriles has been developed using commercially available non-toxic copper acetate as an inexpensive catalyst and ammonium acetate as the
- Bhar, Sanjay,Das, Asit Kumar,Nandy, Sneha
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p. 4605 - 4614
(2022/02/19)
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- 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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- Sustainable and recyclable palladium nanoparticles–catalyzed reduction of nitroaromatics in water/glycerol at room temperature
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Palladium nanoparticles with unique catalytic activity and high stability are synthesized. These nanoparticles exhibit excellent catalytic reduction activity for nitroaromatics in green solvents in the presence of H2 at ambient pressure and temperature. The prominent advantages of this nanotechnology include low consumption of catalyst, excellent chemoselectivity, high reusability of the catalyst, and environmentally green solvents.
- Chen, Jin,Dai, Bencai,Liu, Changchun,Shen, Zhihao,Zhao, Yongde,Zhou, Yang
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p. 540 - 544
(2020/07/14)
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- Revisiting the synthesis of aryl nitriles: a pivotal role of CAN
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Facilitated by the dual role of Ceric Ammonium Nitrate (CAN), herein we report a cost-effective approach for the cyanation of aryl iodides/bromides with CAN-DMF as an addition to the existing pool of combined cyanation sources. In addition to being an oxidant, CAN acts as a source of nitrogen in our protocol. The reaction is catalyzed by a readily available Cu(ii) salt and the ability of CAN to generate ammonia in the reaction medium is utilized to eliminate the additional requirement of a nitrogen source, ligand, additive or toxic reagents. The mechanistic study suggests an evolution of CN?leading to the synthesis of a variety of aryl nitriles in moderate to good yields. The proposed mechanism is supported by a series of control reactions and labeling experiments.
- Saikia, Rakhee,Park, Kwihwan,Masuda, Hayato,Itoh, Miki,Yamada, Tsuyoshi,Sajiki, Hironao,Mahanta, Sanjeev P.,Thakur, Ashim J.
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p. 1344 - 1351
(2021/02/27)
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- Cu-Catalyzed Cross-Coupling of Nitroarenes with Aryl Boronic Acids to Construct Diarylamines
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The development and study of a simple copper-catalyzed reaction of nitroarenes with aryl boronic acids to form diarylamines that uses phenyl silane as the stoichiometric terminal reductant is described. This cross-coupling reaction requires as little as 2 mol % of CuX and 4 mol % of diphosphine for success and tolerates a broad range of functional groups on either the nitroarene or the aryl boronic acid to afford the amine in good yield. Mechanistic investigations established that the cross-coupling reaction proceeds via a nitrosoarene intermediate and that copper is required to catalyze both the deoxygenation of the nitroarene to afford the nitrosoarene and C-NAr bond formation of the nitrosoarene with the aryl boronic acid.
- Guan, Xinyu,Zhu, Haoran,Driver, Tom G.
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p. 12417 - 12422
(2021/10/12)
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- The benzonitrile derivative
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[A] suppressing the generation of impurities caused by side reactions and reaction, and benzonitrile derivative can be obtained in high purity of the benzonitrile derivative method. The compound represented by general formula [a] I, III and IV compound represented by general formula compound represented by a general formula selected from the group consisting of tertiary amines in the presence of at least 1 species is reacted, the benzonitrile derivative represented by general formula II comprises obtaining the benzonitrile derivative. In the general formula I, R1 - R4 Each independently, a hydrogen atom, an alkyl group of carbon number 1 - 5 represent the like, in the general formula II, R21 - R24 Each independently, a hydrogen atom, an alkyl group of carbon number 1 - 5 represent the like, in the general formula III, R31 - R33 Is, each independently represents an alkyl group or a phenyl group, having the general formula IV in, R41 - R44 Is, each independently represents an alkyl group. The details of the code as described herein. [Drawing] no
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Paragraph 0048; 0050-0065
(2021/10/08)
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- Conversions of aryl carboxylic acids into aryl nitriles using multiple types of Cu-mediated decarboxylative cyanation under aerobic conditions
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Here, we used malononitrile or AMBN as a cyanating agent to develop efficient and practical protocols for Cu-mediated decarboxylative cyanations, under aerobic conditions, of aryl carboxylic acids bearing nitro and methoxyl substituents at the ortho position as well as of heteroaromatic carboxylic acids. These protocols involved economical methods to synthesize value-added aryl nitriles from simple and inexpensive raw materials. Further diversification of the 2-nitrobenzonitrile product was performed to highlight the practicality of the protocols. This journal is
- Cai, Hu,Cao, Xihan,Fu, Zhengjiang,Guo, Shengmei,Wang, Shuiliang
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supporting information
p. 8381 - 8385
(2020/11/05)
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- Copper-Catalyzed One-Pot Synthesis of 2,3-Dihydroquinazolin-4(1 H)-ones from 2-Nitrobenzonitriles and Carbonyl Compounds Mediated by Diboronic Acid in Methanol-Water
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A copper-catalyzed one-pot synthesis of 2,3-dihydroquinazolin-4(1 H)-ones with diboronic acid as a reductant in an aqueous medium is described. Various 2,3-dihydroquinazolin-4(1 H)-ones were prepared with good functional-group tolerance in good yields under mild conditions from readily available 2-nitrobenzonitriles and various carbonyl compounds.
- Chen, Yongsheng,Liu, Qixing,Sui, Yuebo,Zhang, Kaili,Zhang, Yin,Zhou, Haifeng
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supporting information
p. 275 - 279
(2020/02/15)
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- Method for reducing aromatic nitro into arylamine
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The invention relates to a method for reducing aromatic nitro to arylamine. The method comprises the following steps: (1) taking an aromatic nitro compound as a raw material, water as a hydrogen source, a palladium compound, cheap and easy to obtain, as a catalyst and tetrahydroxydiboron as an additive to reduce nitro to obtain a product; (2) taking the aromatic nitro compound as the raw material, a copper salt, cheap and easy to obtain, as the catalyst, the tetrahydroxydiboron as the additive to reduce the nitro to obtain a product; and (3) taking the aromatic nitro compound as the raw material, water as the hydrogen source, and the tetrahydroxydiboron as the additive, without needing a metal catalyst, to reduce the nitro to obtain a product. A preparation method for the arylamine, which is provided by the invention, is mild in reaction condition, low in costs, environment-friendly, high in yield, and suitable for industrial production.
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Paragraph 0125-0128; 0225-0228; 0269-0272
(2020/07/15)
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- Commercially Available CuO Catalyzed Hydrogenation of Nitroarenes Using Ammonia Borane as a Hydrogen Source
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Tandem ammonia borane dehydrogenation and nitroarenes hydrogenation has been reported as a novel strategy for the preparation of aromatic amines. However, the practical application of this strategy is subjected to the high-cost and tedious preparation of supported noble metal nanocatalysts. The commercially available CuO powder is herein demonstrated to be a robust catalyst for hydrogenation of nitroarenes using ammonia borane as a hydrogen source under mild conditions. Numerous amines (even sterically hindered, halogenated, and diamines) could be obtained through this method. This monometallic catalyst is characteristic of support-free, excellent chemoselectivity, low-cost, and high recyclability, which will favor its future utilization in preparative reduction chemistry. Mechanistic studies are also carried out to clarify that diazene and azoxybenzene are key intermediates of this heterogeneous reduction.
- Du, Jialei,Chen, Jie,Xia, Hehuan,Zhao, Yiwei,Wang, Fang,Liu, Hong,Zhou, Weijia,Wang, Bin
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p. 2426 - 2430
(2020/03/30)
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- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
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We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
- Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
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p. 378 - 385
(2020/10/02)
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- Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species
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Cyano-containing compounds constitute important pharmaceuticals, agrochemicals and organic materials. Traditional cyanation methods often rely on the use of toxic metal cyanides which have serious disposal, storage and transportation issues. Therefore, there is an increasing need to develop general and efficient catalytic methods for cyanide-free production of nitriles. Here we report the reductive cyanation of organic chlorides using CO2/NH3 as the electrophilic CN source. The use of tridentate phosphine ligand Triphos allows for the nickel-catalyzed cyanation of a broad array of aryl and aliphatic chlorides to produce the desired nitrile products in good yields, and with excellent functional group tolerance. Cheap and bench-stable urea was also shown as suitable CN source, suggesting promising application potential. Mechanistic studies imply that Triphos-Ni(I) species are responsible for the reductive C-C coupling approach involving isocyanate intermediates. This method expands the application potential of reductive cyanation in the synthesis of functionalized nitrile compounds under cyanide-free conditions, which is valuable for safe synthesis of (isotope-labeled) drugs.
- Dong, Yanan,Li, Yuehui,Yang, Peiju,Zhao, Shizhen
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- Palladium-Catalyzed Cyanation of Aryl Halides Using Formamide and Cyanuric Chloride as a New “CN” Source
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A new source of “CN” employing formamide and cyanuric chloride is introduced for the cyanation reactions. The treatment of formamide and 2,4,6-trichloro-1,3,5-triazine (TCT; cyanuric chloride) afforded an efficient cyanating agent which it can be used as a nontoxic, readily available, and non-expensive reagent in the cyanation transformations. In this study, palladium-catalyzed cyanation of aryl halides was successfully accomplished using this new “CN” source in high yields.
- Niknam, Esmaeil,Panahi, Farhad,Khalafi-Nezhad, Ali
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p. 2699 - 2707
(2020/04/08)
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- Preparation method of aminobenzonitrile
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The invention relates to the technical field of fine chemical synthesis, and discloses a preparation method of aminobenzonitrile. Aminobenzamide is taken as a raw material, and aminobenzonitrile is obtained through a three-step reaction of amino protection, dehydration and hydrolysis by taking thionyl chloride as an amino protective agent and a dehydrating agent, The preparation method comprises the following steps: amino protection and dehydration are carried out on aminobenzamide by thionyl chloride in sequence to obtain an amino-protected nitrile organic matter, then water is added to carryout a hydrolysis reaction, and the protective agent on the amino group is removed to obtain the aminobenzonitrile product. The thionyl chloride is used, so the dehydration effect can be achieved, anda new group formed by a reaction of the thionyl chloride with the amino group can play a role in protecting the amino group in the reaction process, thereby the product yield and quality are obviously improved, the reaction temperature is greatly lower than that of a traditional process, the reaction time is obviously shortened, the safety is obviously improved, the operation is simple, the conditions are mild, the method is green and clean, aminobenzonitrile can be efficiently prepared at low cost, and the method is suitable for industrial production.
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Paragraph 0027-0029
(2020/07/02)
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- Method for continuous preparation of nitriles by amides (by machine translation)
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The method comprises the following steps: preparing a lead salt supported by a molecular sieve by a lead salt and a molecular sieve through an impregnation method; and filling a molecular sieve-loaded lead catalyst into a fixed bed reactor. The amide or amide solution is sent into a fixed bed reactor from the top of the fixed bed to be subjected to catalytic dehydration, and the obtained reaction product is led out from the bottom of the fixed bed. The reaction product is separated to obtain the crude product of the nitrile corresponding to the amide. A fixed bed continuous production process is adopted, the reaction process is simple, the production efficiency is high, the product post-treatment is simple, and industrial production is easy to realize. (by machine translation)
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Paragraph 0033-0054; 0061-0065
(2020/12/15)
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- Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
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The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.
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Paragraph 0034-0039; 0154-0159
(2020/09/16)
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- Method for continuous preparation of nitriles in a pipelined reactor (by machine translation)
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The method comprises the following steps that a tin catalyst is coated on the inner wall of the pipeline reactor; and the method comprises the following steps: coating a tin catalyst on the inner wall of the pipeline reactor. The amide solution and the catalytic auxiliary agent are mixed and then sent to a pipeline reactor, and the amide is dehydrated to generate nitrile at the reaction pressure of 0.1 - 2.0 mpa and 100 - 200 °C reaction temperature. The resulting reaction product was separated to give the crude product of the nitrile to which the amide corresponded. In the pipeline reactor, the corresponding nitrile is continuously prepared under the action of the tin catalyst, a dehydrating agent is not needed, byproducts only are water, and three wastes are reduced. (by machine translation)
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Paragraph 0036-0047; 0056; 0058
(2020/12/14)
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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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- Immobilized palladium nanoparticles on a cyclodextrin-polyurethane nanosponge (Pd-CD-PU-NS): An efficient catalyst for cyanation reaction in aqueous media
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Immobilized palladium nanoparticles on a cyclodextrin-polyurethane nanosponge (Pd-CD-PU-NS) were found to be an efficient heterogeneous catalyst in the cyanation reaction of aryl halides in aqueous media. This catalyst system is containing palladium nanoparticles with a size of ~7 nm. Moreover, the CD-PU-NS support formed microsphere-shaped structures with a size of ~100–200 nm. The TEM images show that Pd nanoparticles were formed in near spherical shape morphology and were immobilized in the structure of the CD-PU-NS support. Under our optimized reaction conditions, aryl cyanides were obtained in high yields in the presence of the Pd-CD-PU-NS catalyst. Our results demonstrated that the Pd-CD-PU-NS catalyst is highly effective in the cyanation reaction in aqueous media. Furthermore, the catalyst could be simply extracted from the reaction mixture, providing an efficient methodology for the synthesis of aryl cyanides. The Pd-CD-PU-NS catalyst could be recycled four times with almost consistent catalytic efficiency.
- Khajeh Dangolani, Soheila,Sharifat, Sara,Panahi, Farhad,Khalafi-Nezhad, Ali
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supporting information
p. 256 - 265
(2019/06/07)
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- An Insight into Nitromethane as an Organic Nitrile Alternative Source towards the Synthesis of Aryl Nitriles
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Directed by an unusual in situ reduction of CuII, our protocol is a simple CuI-mediated synthesis of aryl nitriles, with inexpensive and readily available nitromethane as the cyanating source, in moderate to good yields. Exhibiting a wide substrate scope, the method involves simple reaction conditions, is additive free with low catalyst loading. The plausible mechanism of cyanation of aryl halides is elucidated by a congregation of three cycles, namely the in situ reduction of CuII species by nitromethane, generation of HCN species from nitromethane and a regular organometallic pathway which releases the nitrile derivative. The detail of the mechanism of generation of CN– from nitromethane is computationally validated. Our protocol holds the distinction of involving a rarely encountered CuI catalytic species as well as facile in situ generation of nucleophilic CN– to yield synthetically useful aromatic nitriles.
- Saikia, Rakhee,Dey Baruah, Satyajit,Deka, Ramesh C.,Thakur, Ashim J.,Bora, Utpal
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p. 6211 - 6216
(2019/11/05)
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- Metal-free Reduction of Nitro Aromatics to Amines with B 2 (OH) 4 /H 2 O
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A metal-free reduction of nitro aromatics mediated by diboronic acid with water as both the hydrogen donor and solvent under mild conditions has been developed. A series of aromatic amines were obtained with good functional group tolerance and in good yields.
- Chen, Danyi,Zhou, Yanmei,Zhou, Haifeng,Liu, Sensheng,Liu, Qixing,Zhang, Kaili,Uozumi, Yasuhiro
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supporting information
p. 1765 - 1768
(2018/06/26)
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- Cu-catalyzed reduction of azaarenes and nitroaromatics with diboronic acid as reductant
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A ligand-free copper-catalyzed reduction of azaarenes with diboronic acid as reductant in an aprotic solvent under mild conditions has been developed. Most interestingly, the nitroazaarenes could be reduced exclusively to give the corresponding amines without touching the azaarene moieties. Furthermore, the reductive amination of aromatic nitro compounds and aromatic aldehydes has also been realized. A series of hydrogenated azaarenes and secondary amines were obtained with good functional group tolerance.
- Pi, Danwei,Zhou, Haifeng,Zhou, Yanmei,Liu, Qixing,He, Renke,Shen, Guanshuo,Uozumi, Yasuhiro
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p. 2121 - 2129
(2018/03/23)
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- Cyaniding method for preparing nitrile compound
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The invention provides a cyaniding method for preparing a nitrile compound. Organic halide or pseudohalide, CO2 and NH3 which are low in price and are easily obtained and a reducing agent react, a selective cyaniding reaction is conducted in the presence of a transition metal catalyst, and the target product namely organic the nitrile compound is obtained. According to the cyaniding method for preparing the nitrile compound, a new reaction route is used, through a CO2 and NH3 reaction of metal catalysis, dehalogenation cyaniding or quasi halide cyaniding of halide or pseudohalide is directly achieved through a one-pot method, the problem is solved that a traditional cyanation reaction needs equivalent toxic cyanide, a new direct and convenient method for preparing isotope-labeled nitrile compounds is provided at the same time, and the method can be applied to medicine, tracing, biology and medicine research and development.
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Paragraph 0080-0082
(2018/05/30)
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- Controlled Transformations of Aryl Halides in a Flow System: Selective Synthesis of Aryl Azides and Aniline Derivatives
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Copper-mediated nitrogenation of aryl halides with sodium azide can result in either aryl azides or aniline derivatives. The selectivity of the transformation is highly dependent on reaction time and temperature, which led to contradictory literature results with respect to product selectivity and the conditions applied. The advantages of a strictly controlled flow reactor environment were exploited in order to facilitate selective haloarene transformations. Reaction conditions were carefully investigated to understand their role on product selectivity. Aryl azides and aryl amines were successfully prepared from the same starting materials using the same auxiliaries by means of precise control over residence time and reaction temperature, thereby ensuring time-, cost- and atom-efficient syntheses. (Figure presented.).
- Georgiádes, ádám,?tv?s, Sándor B.,Fül?p, Ferenc
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p. 1841 - 1849
(2018/04/09)
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- Catalytic application of 1,3,5-triazine-pentaethylenehexamine polymer-supported palladium nanoparticles in the convenient reduction of nitroarenes with sodium borohydride or hydrazine
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The catalytic activity of 1,3,5-triazine-pentaethylenehexamine (TAPEHA) polymer-supported Pd nanoparticles was investigated in the reduction of nitro arenes to the corresponding amines by NaBH4 or N2H4 .H2 O. Optimized reaction conditions for both systems were successfully tested on 20 nitroarenes with different characteristics. Considerably high yields (80%-98% in NaBH4 and 85%-98% in N2H4) were obtained in a short time and at ambient temperature. In addition to these methods being selective against other reducible functionalities such as -CN, -Br, -Cl, and -I, the catalyst can be recovered easily and reused more than ten times.
- Gen?, Hayriye,Zengin, Mustafa,Kü?ükislamo?lu, Mustafa,Imamoglu, Mustafa,Toplan, Hüseyin ?zkan,Arslan, Mustafa
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p. 784 - 792
(2017/11/20)
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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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- Water as a hydrogen source in palladium-catalyzed reduction and reductive amination of nitroarenes mediated by diboronic acid
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An unprecedented palladium-catalyzed chemoselective reduction and reductive amination of nitroarenes with water as a hydrogen source mediated by diboronic acid have been discovered. A series of aryl amines containing various reducible functional groups were obtained in good to excellent yields.
- Zhou, Yanmei,Zhou, Haifeng,Liu, Sensheng,Pi, Danwei,Shen, Guanshuo
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p. 3898 - 3904
(2017/06/13)
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- Ex situ generation of stoichiometric HCN and its application in the Pd-catalysed cyanation of aryl bromides: Evidence for a transmetallation step between two oxidative addition Pd-complexes
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A protocol for the Pd-catalysed cyanation of aryl bromides using near stoichiometric and gaseous hydrogen cyanide is reported for the first time. A two-chamber reactor was adopted for the safe liberation of ex situ generated HCN in a closed environment, which proved highly efficient in the Ni-catalysed hydrocyanation as the test reaction. Subsequently, this setup was exploited for converting a range of aryl and heteroaryl bromides (28 examples) directly into the corresponding benzonitriles in high yields, without the need for cyanide salts. Cyanation was achieved employing the Pd(0) precatalyst, P(tBu)3-Pd-G3 and a weak base, potassium acetate, in a dioxane-water solvent mixture. The methodology was also suitable for the synthesis of 13C-labelled benzonitriles with ex situ generated 13C-hydrogen cyanide. Stoichiometric studies with the metal complexes were undertaken to delineate the mechanism for this catalytic transformation. Treatment of Pd(P(tBu)3)2 with H13CN in THF provided two Pd-hydride complexes, (P(tBu)3)2Pd(H)(13CN), and [(P(tBu)3)Pd(H)]2Pd(13CN)4, both of which were isolated and characterised by NMR spectroscopy and X-ray crystal structure analysis. When the same reaction was performed in a THF : water mixture in the presence of KOAc, only (P(tBu)3)2Pd(H)(13CN) was formed. Subjection of this cyano hydride metal complex with the oxidative addition complex (P(tBu)3)Pd(Ph)(Br) in a 1 : 1 ratio in THF led to a transmetallation step with the formation of (P(tBu)3)2Pd(H)(Br) and 13C-benzonitrile from a reductive elimination step. These experiments suggest the possibility of a catalytic cycle involving initially the formation of two Pd(ii)-species from the oxidative addition of LnPd(0) into HCN and an aryl bromide followed by a transmetallation step to LnPd(Ar)(CN) and LnPd(H)(Br), which both reductively eliminate, the latter in the presence of KOAc, to generate the benzonitrile and LnPd(0).
- Kristensen, Steffan K.,Eikeland, Espen Z.,Taarning, Esben,Lindhardt, Anders T.,Skrydstrup, Troels
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p. 8094 - 8105
(2017/11/27)
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- Photoinduced Copper(I)-Catalyzed Cyanation of Aromatic Halides at Room Temperature
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The first photoinduced copper(I)-catalyzed cyanation of aromatic halides at room temperature has been developed. The sp2 cyanation reaction exhibits outstanding tolerance to functional groups including primary amines and carboxylic acids, and chemoselectivity to SN2-reactive alkyl chlorides. Mechanistic investigations indicate that the reaction occurs via a single-electron transfer (SET) between the aryl halide and an excited copper(I) cyanide catalytic intermediate. (Figure presented.).
- Kim, Kicheol,Hong, Soon Hyeok
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supporting information
p. 2345 - 2351
(2017/07/22)
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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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- A highly active non-precious metal catalyst based on Fe-N-C@CNTs for nitroarene reduction
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Research on transition metal-nitrogen-carbon (M-N-C) materials revealed their potential as catalysts in several important traditional reactions. However, the activity of M-N-C still needs to be further improved and the real active center of M-N-C catalysts is still under debate. In this work, an efficient Fe-N-C@CNTs for the hydrogenation of nitroarenes was prepared by pyrolysis of FeCl3, phenanthroline and CNTs. Fe-N-C supported on CNTs is much more active than that supported on activated carbon, showing the promotion effect of CNTs. The characterization results suggest that the high activity of Fe-N-C is mainly attributed to the formation of ?-Fe3N, which is the active site for the hydrogenation reaction. Nitrogen/carbon atoms contacted to the active centers could serve as bridges to transport the dissociated hydrogen atoms via spillover effect. The catalytic performance of Fe-N-C was also tested on fixed bed reactor under continuous flow condition for the first time and could smoothly catalyze the reaction for over 300 hours.
- Chen, Jian,Yao, Yi,Zhao, Jiao,Zhao, Yaopeng,Zheng, Yuanyuan,Li, Mingrun,Yang, Qihua
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p. 96203 - 96209
(2016/10/22)
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- Vasicine from Adhatoda vasica as an organocatalyst for metal-free Henry reaction and reductive heterocyclization of o-nitroacylbenzenes
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Vasicine, a quinazoline alkaloid, from the leaves of Adhatoda vasica, has been utilized as an efficient catalyst for metal and base free Henry reaction of various aldehydes with nitro alkanes. The method can be used in the synthesis of various β-nitro alcohols under mild reaction conditions without use of hazardous organic solvents and expensive catalysts. Vasicine is also applied successfully for one pot synthesis of 2,1-benzisoxazoles from o-nitroacylbenzenes in good yields under mild conditions.
- Sharma, Sushila,Kumar, Manoranjan,Bhatt, Vinod,Nayal, Onkar S.,Thakur, Maheshwar S.,Kumar, Neeraj,Singh, Bikram,Sharma, Upendra
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supporting information
p. 5003 - 5008
(2016/10/25)
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- Graphene-Supported NiPd Alloy Nanoparticles for Effective Catalysis of Tandem Dehydrogenation of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds
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Monodisperse NiPd alloy nanoparticles (NPs) are synthesized and assembled on graphene (G) or other support to provide clean, efficient catalysis of tandem reactions—dehydrogenation of ammonia borane (AB) and hydrogenation of R—NO2 and/or R—CN to R—NH2. The tandem reactions proceed quickly and with high efficiency in aqueous methanol solutions at room temperature, and the supported catalyst is readily recovered for re-use, providing a simple, efficient and ‘green’ route to the preparation of many common pharmaceutical, dye or other chemical products. NiPd alloy NPs of 3.4 nanometer size were prepared by co-reduction of nickel(II) acetate and palladium(II) acetlyacetonate by borane-tert-butylamine in oleylamine and deposited on G via a solution phase self-assembly process. The G-NiPd showed composition-dependent catalysis on the tandem reaction with G-Ni30Pd70 being the most active. A variety of R—NO2 and/or R—CN derivatives (R alkyl or aryl) were reduced selectively into R—NH2 via G-Ni30Pd70 catalyzed tandem reaction in short (5-30 minute) reaction times with conversion yields reaching up to 100%, demonstrating a new approach to G-NiPd-catalyzed dehydrogenation of AB and hydrogenation of R—NO2 and R—CN. The G-NiPd NP catalyst is efficient and is reusable; thus the reaction can be performed in an environment-friendly process with short reaction times and high yields.
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Paragraph 0022
(2016/10/17)
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- Recyclable aluminium oxy-hydroxide supported Pd nanoparticles for selective hydrogenation of nitro compounds via sodium borohydride hydrolysis
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The reduction of aromatic/aliphatic nitro compounds to primary amines with high yields was easily realized by transfer hydrogenation comprising commercially available aluminium oxy-hydroxide-supported Pd nanoparticles (0.5 wt% Pd, Pd/AlO(OH)) as catalysts and NaBH4 as the hydrogen reservoir at room temperature in a water/methanol mixture (v/v = 7/3). The presented catalytic methodology is highly efficient for the reduction of various nitro compounds as well as reusable. A variety of R-NO2 derivatives were tested by performing the Pd/AlO(OH) catalysed reduction reaction and all the nitro compounds were selectively reduced to their corresponding primary amines in reaction times ranging from 0.75 to 13 min with yields reaching up to 99%. This process can be assessed as an eco-friendly method involving both reusable catalysts (Pd/AlO(OH) NPs) and hydrogen sources (NaBH4).
- G?ksu, Haydar
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p. 8498 - 8504
(2015/11/10)
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- Efficient reductions of various nitroarenes with scrap automobile catalyst and NaBH4
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The effect of scrap automobile catalyst (SAC), a waste material, was investigated as a catalyst for the reduction of nitroarenes to the corresponding amines with sodium borohydride in aqueous ethanol at 5-25 °C. Along with the observed high conversions, the SAC and NaBH4 combination also exhibits a selectively catalyzed reduction in compounds containing other reducible functionalities, such as CN, Br, Cl and I. Recycling automobile wastes into a catalyst for organic reactions will offer both environmental protection and economic advantages. As a result, an effective, easy to use, low-priced and reliable method has been developed.
- Genc, Hayriye
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- In Situ-Generated Co0-Co3O4/N-Doped Carbon Nanotubes Hybrids as Efficient and Chemoselective Catalysts for Hydrogenation of Nitroarenes
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The earth-abundant nanohybrids Co0/Co3O4@N-doped carbon nanotubes were fabricated via an efficient thermal condensation of d-glucosamine hydrochloride, melamine, and Co(NO3)2·6H2O. The hybrids furnish excellent catalytic activity and perfect chemoselectivity (>99%) for a wide range of substituted nitroarenes (21 examples) under relatively mild conditions. The high catalytic performance and durability is attributed to the synergistic effects between each component, the unique structure of graphene layers-coated Co0, and the electronic activation of doped nitrogen. Density functional calculations indicate that the inner Co0 core and N species on the carbon shell can significantly decrease the dissociation energies of H2, giving evidence of the ability of carbon shell in the hybrids to enable H2 activation. These results open up an avenue to design more powerful low-cost catalysts for industrial applications.
- Wei, Zhongzhe,Wang, Jing,Mao, Shanjun,Su, Diefeng,Jin, Haiyan,Wang, Yihe,Xu, Fan,Li, Haoran,Wang, Yong
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p. 4783 - 4789
(2015/08/18)
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- Iron(III) Chloride-Catalyzed Decarboxylative-Deaminative Functionalization of Phenylglycine: A Tandem Synthesis of Quinazolinones and Benzimidazoles
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The first iron(III) chloride-catalyzed decarboxylative-deaminative functionalization of phenylglycine with o-substituted nitroarenes was achieved for the synthesis of 4(3H)-quinazolinones and benzimidazoles. The reaction of 2-nitrobenzonitrile/2-nitro-N,N-diphenylamine with phenylglycine at 120 C in the presence of potassium carbonate as a base in toluene generated the products in 45-87% yields. Various functional groups like nitro, fluoride, chloride and trifluoromethyl were well tolerated under the present reaction conditions. In this tandem approach, involvement of transfer hydrogenation of the nitro functionality with in situ generated ammonia, imination, nitrile hydration to amide and oxidative cyclization sequences have been established. The process avoids the use of an external hydrogen source, costly catalysts as well as the isolation of amine and amide intermediates.
- Kumar, Manoranjan,Richa,Sharma, Sushila,Bhatt, Vinod,Kumar, Neeraj
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p. 2862 - 2868
(2015/09/28)
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- A Mild and Chemoselective Reduction of Nitro and Azo Compounds Catalyzed by a Well-Defined Mo3S4 Cluster Bearing Diamine Ligands
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Herein, we report a novel well-defined diamino Mo3S4-based catalyst system for the reduction of nitroarenes and azo compounds to the corresponding anilines with silanes as reducing agents. This catalytic protocol provides a facile route to access aromatic amines under mild conditions in good to excellent yields. Notably, even anilines functionalized with other potentially reducible moieties are obtained with high selectivity. The new chemoselective catalyst of formula [Mo3S4Cl3(dmen)3](BF4) (dmen: N,N′-dimethylethylenediamine) is conveniently synthesized through coordination of the diamine ligand to the incomplete Mo3S4 cubane-type cluster core in a one-pot two-step procedure. The crystal structure of the [Mo3S4Cl3(dmen)3]+ cation confirms the formation of a single isomer in which the chlorine atom lies trans to the bridging sulfur atom to afford a C3 symmetry complex with intrinsic backbone chirality. The structure is preserved in solution, as evidenced by multinuclear NMR spectroscopy and electrospray-ionization mass spectrometric techniques.
- Pedrajas, Elena,Sorribes, Iván,Junge, Kathrin,Beller, Matthias,Llusar, Rosa
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p. 2675 - 2681
(2015/09/15)
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- Palladium/N-Heterocyclic carbene catalyzed mono- and double-cyanation of aryl halides using potassium ferrocyanide trihydrate under aerobic conditions
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Abstract A practical palladium/N-heterocyclic carbene catalyzed procedure for the mono- and double-cyanation of aryl halides is described using inexpensive, easy-to-handle and nontoxic potassium ferrocyanide trihydrate {K4[Fe(CN)6]·3H2O} as the cyanating agent. The reaction does not require an anhydrous solvent, or the exclusion of air or moisture. A variety of electron-rich and electron-deficient aryl halides are efficiently converted into their corresponding nitriles and dicarbonitriles.
- Xu, Zhicheng,Xiao, Yunqing,Ding, Hong,Cao, Changsheng,Li, Haitao,Pang, Guangsheng,Shi, Yanhui
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p. 1560 - 1566
(2015/06/02)
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- Stable palladium nanoparticles catalyzed synthesis of benzonitriles using K4[Fe(CN)6]
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A stable palladium nanocatalyst is used in the synthesis of benzonitriles by cyanation of aryl iodides. A nontoxic and economic potassium hexacyanoferrate was used as a safe cyanide source. A variety of benzonitriles are efficiently synthesized using the stable nanocatalyst. The catalyst was quantitatively recovered and reused without any apparent loss in the catalytic activity.
- Ganapathy, Dhandapani,Kotha, Surya Srinivas,Sekar, Govindasamy
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supporting information
p. 175 - 178
(2015/02/02)
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- Exploring the Catalytic Reactivity of Nickel Phosphine-Phosphite Complexes
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In this study, we present an investigation into various nickel phosphite and phosphite-phosphine complexes for use in the Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions and the ammonia arylation reaction. In these coupling reactions, it was discovered that the Ni[P(OEt)3]4, (dppf)Ni[P(OPh)3]2, and (binap)Ni[P(OPh)3]2 catalysts were the most effective. In addition, an optimisation process for these catalytic systems as well as functional group compatibility are discussed.
- Kampmann, Sven S.,Man, Nikki Y. T.,McKinley, Allan J.,Koutsantonis, George A.,Stewart, Scott G.
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p. 1842 - 1853
(2015/12/26)
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- Visible-light-mediated efficient conversion of aldoximes and primary amides into nitriles
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A photosensitization-based approach for a convenient and efficient conversion of aldoximes and primary amides into nitriles is reported. The protocol involves eosin Y catalysed, visible-light-mediated in situ formation of the Vilsmeier-Haack reagent from CBr4 and a catalytic amount of DMF, which brings about the desired transformation to afford nitriles at r.t.
- Yadav, Arvind K.,Srivastava, Vishnu P.,Yadav, Lal Dhar S.
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p. 4181 - 4186
(2014/01/06)
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- Tandem dehydrogenation of ammonia borane and hydrogenation of nitro/nitrile compounds catalyzed by graphene-supported NiPd alloy nanoparticles
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We report a facile synthesis of monodisperse NiPd alloy nanoparticles (NPs) and their assembly on graphene (G) to catalyze the tandem dehydrogenation of ammonia borane (AB) and hydrogenation of R-NO2 and/or R-CN to R-NH2 in aqueous methanol solutions at room temperature. The 3.4 nm NiPd alloy NPs were prepared by coreduction of nickel(II) acetate and palladium(II) acetlyacetonate by borane-tert-butylamine in oleylamine and deposition on G via a solution phase self-assembly process. G-NiPd showed composition-dependent catalysis on the tandem reaction with G-Ni 30Pd70 being the most active. A variety of R-NO 2 and/or R-CN derivatives were reduced selectively into R-NH 2 via G-Ni30Pd70 catalyzed tandem reaction in 5-30 min reaction time with the conversion yields reaching up to 100%. Our study demonstrates a new approach to G-NiPd-catalyzed dehydrogenation of AB and hydrogenation of R-NO2 and R-CN. The G-NiPd NP catalyst is efficient and reusable, and the reaction can be performed in an environment-friendly process with short reaction times and high yields.
- Goeksu, Haydar,Ho, Sally Fae,Metin, Oender,Korkmaz, Katip,Mendoza Garcia, Adriana,Gueltekin, Mehmet Serdar,Sun, Shouheng
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p. 1777 - 1782
(2014/06/24)
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- Palladium-catalyzed cyanation of aryl bromides with malononitrile via acarbon-nitrile bond cleavage mediated by copper
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An efficient palladium catalytic system is developed for the cyanation of aryl bromides using malononitrile as a cheap, less toxic, stable and easy-to-handle 'nonmetallic' cyanide source, which proceeds via copper-catalyzed cleavage of carbon-nitrile (C-CN) bonds. The approach provides a novel and alternative route leading to aryl nitriles. Georg Thieme Verlag Stuttgart New York.
- Lu, Guo-Ping,Bu, Mei-Jie,Cai, Chun
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supporting information
p. 547 - 550
(2014/03/21)
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- Catalytic activation of hydrazine hydrate by gold nanoparticles: Chemoselective reduction of nitro compounds into amines
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Supported gold nanoparticles (2NH2 as a transfer hydrogenation agent. Aryl and alkyl nitro compounds are cleanly and selectively reduced into the corresponding amines in the presence of 4 equivalents of hydrazine. The reaction tolerates other potentially reducible functionalities such as carboxylate, carbonyl, cyano or halides which remain intact.
- Gkizis, Petros L.,Stratakis, Manolis,Lykakis, Ioannis N.
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- Efficient palladium-catalyzed cyanation of aryl/heteroaryl bromides with K4[Fe(CN)6] in t-BuOH-H2O using tris(2-morpholinophenyl)phosphine as a ligand
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A practical method for the synthesis of various aryl/heteroaryl nitriles using non-toxic K4[Fe(CN)6] as the cyanide source is described. The cyanation of aryl/heteroaryl bromides with K4[Fe(CN) 6] proceeded smoothly in the presence of a Pd/tris(2- morpholinophenyl)phosphine (L5) catalyst under mild conditions. The corresponding aryl/heteroaryl nitriles were produced in good to excellent yields. The Royal Society of Chemistry 2013.
- Zou, Tao,Feng, Xiujuan,Liu, Hesong,Yu, Xiaoqiang,Yamamoto, Yoshinori,Bao, Ming
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p. 20379 - 20384
(2013/11/06)
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