- Metalloporphyrin catalyzed oxidation of N-hydroxyguanidines: A biomimetic model for the H2O2-dependent activity of nitric oxide synthase
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A chemical model for the H2O2 promoted oxidation by nitric oxide synthase (NOS) has been developed. Biomimetic oxidations were carried out using H2O2 and tetrakis(perfluorophenyl)porphyrinato-iron(III) chloride (FeTPPF20) as a catalyst. Similarly to NOS our model system produces N(δ)-cyanoornithine, citrulline and NO from NOHA and did not oxidize arginine itself. Based on these results we propose a peroxide shunt to be involved in the catalytic cycle of NOS. To the best of our knowledge this is the first chemical system that semiquantitatively mimics NOS activity. (C) 2000 Elsevier Science Ltd. All rights reserved.
- Keseru, Gyoergy M.,Balogh, Gyoergy T.,Karancsi, Tamas
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- Highly efficient synthesis of primary amides: Via aldoximes rearrangement in water under air atmosphere catalyzed by an ionic ruthenium pincer complex
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The transformation of aldoximes to primary amides has been evaluated using pincer ruthenium complexes a-c, among which the ionic Ru catalyst a proved to be the most efficient in water under air atmosphere. A variety of (hetero)arene aldoximes proceeded smoothly to afford amides in high yields with good functional group compatibilities. Furthermore, a direct synthetic route of amides from aldehydes, hydroxylamine hydrochloride and sodium carbonate was also described with broad substrates including conjugated and aliphatic aldehydes. This protocol is operationally simple and proceeds with a low catalyst loading (0.5 mol%).
- Yang, Fa-Liu,Zhu, Xinju,Rao, Dun-Kang,Cao, Xiao-Niu,Li, Ke,Xu, Yan,Hao, Xin-Qi,Song, Mao-Ping
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- Rhenium(VII) oxo complexes as extremely active catalysts in the dehydration of primary amides and aldoximes to nitriles
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An economical and environmentally benign process for the preparation of nitriles by the dehydration of primary amides and aldoximes is catalyzed by rhenium(VII) oxo complexes such as perrhenic acid and trimethylsilylperrhenate (see scheme). The reaction proceeds at azeotropic reflux (with the removal of water) under essentially neutral conditions.
- Ishihara, Kazuaki,Furuya, Yoshiro,Yamamoto, Hisashi
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- An indium mediated efficient chemoselective deoxygenation of N-oxides and nitrones
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A simple and inexpensive procedure for the deoxygenation of N-oxides, such as N-arylnitrones, azoxybenzenes and N-heteroarene N-oxides with indium trichloride in acetonitrile at ambient pressure is described. The procedure gives high yields of deoxygenated products.
- Ilias, Md,Barman, Dhiren C,Prajapati, Dipak,Sandhu, Jagir S
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- 1-Cyanoimidazole as a mild and efficient electrophilic cyanating agent
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formula presented A mild and high-yielding cyanating reaction of amine, sulfur, and carbanion nucleophiles is reported here using 1-cyanoimidazole as an electrophilic cyanating agent.
- Wu, Yong-Qian,Limburg, David C.,Wilkinson, Douglas E.,Hamilton, Gregory S.
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- Ternary VZrALON oxynitrides - Efficient catalysts for the ammoxidation of 3-picoline
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Starting from previous binary VZrON (VAlON) oxynitrides with high (low) activity and low (high) selectivity, a new class of ternary VZrAlON catalysts has been developed for the ammoxidation of 3-picoline to 3-cyanopyridine (3-CP), which combine the benefi
- Janke, Christiane,Radnik, J?rg,Bentrup, Ursula,Martin, Andreas,Brückner, Angelika
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- Dispersion and 3-Picoline Ammonoxidation Investigation of V2O5/α-Al2O3 Catalysts
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The effect of changing the precursor on the dispersion and 3-picoline ammonoxidation activity of various α-Al2O3 supported V2O5 catalysts has been investigated by the techniques of X-ray fluorescence, AES, SEM, EPR, XRD, oxygen chemisorption at 195 K and
- Reddy, Benjaram Narasimha,Reddy, Benjaram Mahipai,Subrahmanyam, Machiraju
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- Statistical experimental design-driven discovery of room-temperature conditions for palladium-catalyzed cyanation of aryl bromides
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A combination of Pd2(dba)3·CHCl3 (0.5 mol %) and commercially available, air-stable phosphonium salt [(t-Bu) 3PH]BF4 (1.4 mol %) in a presence of Zn powder and Zn(CN)2 as the cyanide source comprises an extremely efficient catalyst system for the cyanation of a diverse array of aryl bromides, at room temperature. This result emerged from an experimental strategy that combines the advantages of parallel, automated experimentation with the design of experiments (DOE) for the effective definition of an optimal set of reaction conditions.
- Stazi, Federica,Palmisano, Giovanni,Turconi, Marco,Santagostino, Marco
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- Perrhenic acid-catalyzed dehydration from primary amides, aldoximes, N-monoacylureas, and α-substituted ketoximes to nitrile compounds
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The dehydration reaction of primary amides is one of the most fundamental methods for the synthesis of nitriles, and the development of environmentally benign catalytic reaction processes is needed. We surveyed a variety of metal catalysts and found that perrhenic acid was extremely effective for the dehydration of not only primary amides but also aldoximes. Typically, 1 mol % of perrhenic acid gave the corresponding nitriles from amides or aldoximes under azeotropic reflux conditions with the removal of water in toluene or mesitylene. In addition, perrhenic acid is an extremely efficient catalyst for the Beckmann fragmentation of α-substituted ketoximes to functionalized nitriles. This new catalytic system can be applied to the gram-scale synthesis of nitriles without further modifications.
- Furuya, Yoshiro,Ishihara, Kazuaki,Yamamoto, Hisashi
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- Iodine/aqueous NH4OAc: An improved reaction system for direct oxidative conversion of aldehydes and alcohols into nitriles
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A convenient method for direct oxidative conversion of aldehydes and alcohols into nitriles has been developed by using the inexpensive and environmentally friendly reagent I2/aqueous NH4OAc. The aqueous NH4OAc as a non-toxic cyanide source is more eco-friendly than aqueous ammonia, because gaseous ammonia evaporates easily from aqueous ammonia but not from aqueous NH4OAc.
- Ren, Yi-Ming,Zhu, Yi-Zhong,Cai, Chun
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- A Selective and Mild Oxidation of Primary Amines to Nitriles with Trichloroisocyanuric Acid
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An efficient and highly selective method for the oxidative conversion of primary amines to the corresponding nitriles using trichloroisocyanuric acid in the presence of catalytic TEMPO under mild reaction conditions is described. Other functional groups such as C,C-double bonds, benzyloxy etc. were found to be unaffected under the reaction conditions. This procedure provides a new entry to the synthesis of various aliphatic, aromatic and heterocyclic nitriles in excellent yield.
- Chen, Fen-Er,Kuang, Yun-Yan,Dai, Hui-Fang,Lu, Liang,Huo, Ming
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- Exploration of relative chemoselectivity in the hydrodechlorination of 2-chloropyridines
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The chemoselectivity of hydrodechlorination in 2-chloropyridine derivatives possessing reduction-sensitive functionalities is examined. The reaction conditions employed tolerate a variety of functionalities illustrating highly chemoselective hydrodechlorination in the presence of nitrile, allyl, terminal olefin, and nitroamine functionalities in excellent yield. Chemoselective deprotection of carboxybenzyl ethers is illustrated in moderate yield.
- Kinarivala, Nihar,Trippier, Paul C.
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- Hydrothermal synthesis of microporous W-V-O as an efficient catalyst for ammoxidation of 3-picoline
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W-V complex metal oxide (W-V-O) was prepared by hydrothermal synthesis method. Characterization by XRD, XPS, ICP-AES, N2 adsorption, and STEM showed that W-V-O had a layered structure with micropore. W-V-O was tested for the vapor phase ammoxid
- Goto, Yoshinori,Shimizu, Ken-Ichi,Murayama, Toru,Ueda, Wataru
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- bis(trichloromethyl)carbonate, an efficient activator for the one-pot conversion of aldehydes into nitriles under mild conditions
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A single step conversion of aldehydes into the corresponding nitriles has been achieved in high yields using stoichiometric amounts of NH2OH·HCl, Et3N and bis(trichloromethyl)-carbonate at room temperature.
- Bose, D. Subhas,Goud, P. Ravinder
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- Potassium hexacyanoferrate(II) - A new cyanating agent for the palladium-catalyzed cyanation of aryl halides
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A new advantageous cyanating agent, potassium hexacyanoferrate(II), is described for the palladium-catalyzed cyanation of aryl halides. All cyanide ions on the iron(II) center can be transferred to the aryl halide using palladium(II) acetate and dppf as the catalyst. Under optimized reaction conditions good yields of benzonitriles and unprecedented catalyst productivities are observed.
- Schareina, Thomas,Zapf, Alexander,Beller, Matthias
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- Characterization and reactivity of molybdenum oxide catalysts supported on niobia
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A series of MoO3/Nb2O5 catalysts with Mo loadings varying from 2.5 to 15 wt% were prepared and characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), temperature-programmed desorption (TPD) of am
- Chary, Komandur V.R.,Bhaskar, Thallada,Kishan, Gurram,Reddy, Kondakindi Rajender
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- A simple method for the synthesis of nitriles from primary amides under neutral conditions
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1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI) is a very useful reagent for the preparation of nitriles in good yields under neutral conditions.
- Bose, D. Subhas,Sunder, K. Sugnana
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- A Novel Single Step Synthesis of Nicotinamide by β-Picoline Ammoxidation over MoO3 and CuO Oxide Catalysts
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Ammonia up-take has been correlated directly, for the first time, with the selective formation of nicotinamide on MoO3 and CuO; nicotinonitrile on V2O5; CO2 and H2O on Bi2O3 catalysts, with a possible mechanism during ammoxidation of β-picoline.
- Reddy, B. Mahipal,Subrahmanyam, M.
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- TrocCl mediated efficient synthesis of nitriles from primary amides
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In order to establish a rapid conversion method of primary amides to nitriles, various types of carboxamides were treated with 2,2,2- trichloroethyl chloroformate and Et3N, as a dehydrating agent to obtain the desired nitriles in 82-95% yields.
- Bose, D. Subhas,Kumar, K. Kiran
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- Decarbonylative Synthesis of Aryl Nitriles from Aromatic Esters and Organocyanides by a Nickel Catalyst
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A decarbonylative cyanation of aromatic esters with aminoacetonitriles in the presence of a nickel catalyst was developed. The key to this reaction was the use of a thiophene-based diphosphine ligand, dcypt, permitting the synthesis of aryl nitrile without the generation of stoichiometric metal- or halogen-containing chemical wastes. A wide range of aromatic esters, including hetarenes and pharmaceutical molecules, can be converted into aryl nitriles.
- Iizumi, Keiichiro,Kurosawa, Miki B.,Isshiki, Ryota,Muto, Kei,Yamaguchi, Junichiro
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- A convenient procedure for the palladium-catalyzed cyanation of aryl halides
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A useful source of cyanide for the palladium-catalyzed cyanation of aryl halides is acetone cyanohydrin (see scheme; dpppe = 1,5-bis(diphenylphosphanyl) pentane, tmeda = N,N,N′,N′-tetramethylethylenediamine). The key to the success of the reaction is the slow dosage of the cyanation reagent to the reaction mixture to prevent the deactivation of the palladium catalyst caused by excess cyanide ions in solution.
- Sundermeier, Mark,Zapf, Alexander,Beller, Matthias
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- Chemistry of α-Amino Nitriles. Exploratory Experiments on Thermal Reactions of α-Amino Nitriles
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The paper extends a previously published report on chemical properties of α-amino nitriles and of members of the C3H4N2 ensemble (Scheme 1) as observed in experiments carried out under non-aqueous conditions.The reactions investigated and the observations made are summarized in some detail in the English footnotes (*) referring to Schemes 1-17 and Fig. 1.
- Xiang, Yi-Bin,Drenkard, Susanne,Baumann, Karl,Hickey, Deirdre,Eschenmoser, Albert
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- Aryl chlorothionoformate: A new versatile reagent for the preparation of nitriles and isonitriles under mild conditions
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Aryl chlorothionoformate is a very useful reagent for the preparation of nitriles and isonitriles in high yields under essentially neutral conditions.
- Subhas Bose,Ravinder Goud
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- Transformation of alkaloid anabasin into nicotinonitrile
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The possibility of preparing nicotinonitrile from the natural alkaloid anabasin via oxidative ammonolysis using a vanadium - titanium catalyst (V2O5:TiO2 = 1.0:0.5) is examined.
- Iskakova,Kagarlitskii
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- Sulfate additives generate robust and highly active palladium catalysts for the cyanation of aryl chlorides
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The use of sulfate additives such as H2SO4 greatly increases the reactivity of palladium catalysts for the cyanation of aryl and heteroaryl chlorides and renders them more robust toward adventitious air. Using this method, a wide variety of aromatic and heteroaromatic nitriles were prepared in high yield.
- Shevlin, Michael
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- Triphenylphosphine-iodine: An efficient reagent system for the synthesis of nitriles from aldoximes
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A wide range of aldoximes were smoothly converted to the corresponding nitriles with triphenylphosphine-iodine. Copyright Taylor & Francis LLC.
- Venkat Narsaiah,Sreenu,Nagaiah
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- A versatile protocol for copper-catalyzed cyanation of aryl and heteroaryl bromides with acetone cyanohydrin
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A novel copper-catalyzed cyanation of aryl and heteroaryl bromides using acetone cyanohydrin has been developed. Copyright
- Schareina, Thomas,Zapf, Alexander,Cotte, Alain,Gotta, Matthias,Beller, Matthias
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- Development of Pd/C-catalyzed cyanation of Aryl halides
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A practical method for palladium-catalyzed cyanation of aryl halides using Pd/C is described. The new method can be applied to a variety of aryl bromide and active aryl chloride substrates to effect efficient conversions. The process features many advantages over existing cyanation conditions and the practical utility of the process has been demonstrated on scale.
- Yu, Hannah,Richey, Rachel N.,Miller, William D.,Xu, Jiansheng,May, Scott A.
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- Ammoxidation of 3-Picoline to Nicotinonitrile over Highly Dispersed V2O5/ZrO2 Catalysts
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Vapour phase ammoxidation of 3-picoline to nicotinonitrile was carried out on highly dispersed vanadia catalysts supported on zirconia, the results suggest that vanadia/zirconia possesses high activity and selectivity for nicotinonitrile formation.
- Chary,Kishan,Narayana,Bhaskar
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- Rapid cyanation of aryl iodides in water using microwave promotion
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We show that using water in conjunction with microwave heating it is possible to prepare aryl nitriles from the corresponding aryl iodides rapidly and in high yield without the need for a palladium catalyst.
- Arvela, Riina K.,Leadbeater, Nicholas E.,Torenius, Hanna M.,Tye, Heather
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- Synthesis, characterization and catalytic performance of titania supported VPO catalysts for the ammoxidation of 3-picoline
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Series of vanadium phosphorus oxide (VPO) catalysts supported over titania (anatase) were synthesised with varying contents of VPO (5-50 wt%). These solids were characterised by ICP-OES, TG/DTA, BET, XRD, FTIR (Py-ads) and XPS. The catalytic activity was
- Kalevaru,Madaan,Martin
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- FTIR study of β-picoline and pyridine-3-carbaldehyde transformation on V-Ti-O catalysts. the effect of sulfate content on β-picoline oxidation into nicotinic acid
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Surface complexes of β-picoline, 3-pyridine-carbaldehyde and nicotinic acid on 20 wt.% V2O5/TiO2 catalysts containing 0.07 and 6.3l wt.% SO42- were studied by FTIR spectroscopy and temperature program
- Chesalov, Yuriy A.,Andrushkevich, Tamara V.,Sobolev, Vladimir I.,Chernobay, Galina B.
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- A practical synthesis of highly functionalized aryl nitriles through cyanation of aryl bromides employing heterogeneous Pd/C: In quest of an industrially viable process
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Preparation of aryl nitrile 2a through classical Rosenmund-von Braun reaction of aryl bromide 1a resulted in a poor yield (61%) due to a high reaction temperature (165°C) and a lack of efficient procedure for separating 2a from a large quantity of heavy metal waste (Cu salts). To address these issues, a practical synthesis of multifunctional aryl nitriles through cyanation of aryl bromides has been developed with heterogeneous Pd/C used as the catalyst. Treatment of aryl bromides 1 with Zn(CN)2 in the presence of Pd/C, Zn, ZnBr2 and PPh3 in DMA provided aryl nitriles 2 involving those carrying sterically demanding electron-rich substituent in good yields and in highly reproducible manner. The activity of Pd/C is highly dependent on the properties of the Pd/C. Oxidic thickshell type catalyst Pd/C D5 was found to furnish the highest rate acceleration and yield. The use of heterogeneous Pd/C might anchor and disperse Pd over the solid support of the catalyst, at least in the initial stage of the reaction, to assure the formation of monomeric Pd complex without precipitating to inactive Pd black. The use of a slightly excess of Zn(CN)2 (0.6 equiv) and air oxidation of phosphine ligand, after end of the reaction, converted Pd species to insoluble phosphine-free Pd cyanides, from which Pd was recovered in high yield through simple filtration followed by usual recovery process involving combustion.
- Hatsuda, Masanori,Seki, Masahiko
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- A SIMPLE REDUCTION OF AROMATIC HETEROCYCLIC N-OXIDES WITH HEXAMETHYLDISILANE: REACTIONS WITH HEXAMETHYLDISILANE AND FLUORIDE ION I
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Aromatic heterocyclic N-Oxides are readily reduced at room temperature by hexamethyldisilane in the presence of fluoride ion in THF.
- Vorbrueggen, Helmut,Krolikiewicz, Konrad
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- A practical synthesis of highly functionalized aryl nitriles through cyanation of aryl bromides employing heterogeneous Pd/C
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An industrially viable cyanation of aryl bromides with Zn(CN)2 was accomplished in the presence of inexpensive and readily accessible Pd/C, Zn dust, ZnBr2, and PPh3 in DMA to provide functionalized aryl nitriles in moderate to high yields.
- Hatsuda, Masanori,Seki, Masahiko
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- Preparation of nitriles from primary amides under Swern oxidation conditions
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In order to establish a mild conversion method of primary amides to nitriles, various types of carboxamides were heated under Swern oxidation conditions, (COCl)2-DMSO and Et3N, as a dehydrating agent to obtain desired nitriles in 75-96% yields.
- Nakajima, Noriyuki,Ubukata, Makoto
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- Effect of reaction medium on the composition of vanadium-titanium catalyst in oxidative ammonolysis of alkylpyridines
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The influence exerted by the concentration of alkylpyridines on the chemical composition of a vanadium-titanium catalyst under oxidative ammonolysis conditions was subjected to a comparative study.
- Saurambaeva,Sembaev
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- The Semmler-Wolff Aromatization and Schmidt Reaction Applied to Some Pyridopyrazolobenzotriazines
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Pyridopyrazolobenzotriazin-4(1H)ones were transformed via their oximes in a Semmler-Wolff aromatization process in the tetracyclic heteroaromatic amines 4 or by Schmidt reaction into a mixture of the same amine 4 and a ring enlarg
- Kocevar, Marijan,Stanovnik, Branko,Tisler, Miha
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- Ammoxidation of 3-picoline to nicotinonitrile using silica-supported VCrO catalysts
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A series of vanadium-chromium oxide (VCrO) catalysts supported on silica was prepared by wetness impregnation method with different Cr/V molar ratios from 0.2 to 1.0. These catalysts were characterized by XRD, TG, temperature-programmed desorption of ammo
- Jiang, Feng,Wei, Ruiping,Gao, Lijing,Xiao, Guomin,Niu, Lei
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- A facile microwave-assisted palladium-catalyzed cyanation of aryl chlorides
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We report an efficient method for the preparation of aryl nitriles from aryl chlorides under either microwave assisted or thermal conditions. A catalyst system comprising tris(dibenzylidene acetone)dipalladium (Pd2(dba)3) and 2-(2′,6′-dimethoxybiphenyl)dicyclohexylphosphine (S-Phos) is shown to effectively promote cyanation of various aryl chlorides with Zn(CN)2 as the cyanide source.
- Chobanian, Harry R.,Fors, Brett P.,Lin, Linus S.
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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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- Palladium-catalyzed synthesis of nitriles from N-phthaloyl hydrazones
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The Pd-catalyzed transformation of N-phthaloyl hydrazones into nitriles involving the cleavage of an N-N bond is reported. The use of N-heterocyclic carbene as a ligand is essential for the success of the reaction. N-Phthaloyl hydrazones prepared from aromatic aldehydes or cyclobutanones are applicable to this transformation, which gives aryl or alkenyl nitriles, respectively.
- Ano, Yusuke,Chatani, Naoto,Higashino, Masaya,Yamada, Yuki
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supporting information
p. 3799 - 3802
(2022/04/07)
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- Recyclable and Reusable Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O System for Cyanation of Aryl Chlorides with Potassium Ferrocyanide
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Pd(OAc)2/XPhos–SO3Na in a mixture of poly(ethylene glycol) (PEG-400) and water is shown to be a highly efficient catalyst for the cyanation of aryl chlorides with potassium ferrocyanide. The reaction proceeded smoothly at 100 or 120?oC with K2CO3 or KOAc as base, delivering a variety of aromatic nitriles in good to excellent yields. The isolation of the crude products is facilely performed by extraction with cyclohexane and more importantly, both expensive Pd(OAc)2 and XPhos–SO3Na in PEG-400/H2O system could be easily recycled and reused at least six times without any apparent loss of catalytic efficiency. Graphical Abstract: Palladium-catalyzed cyanation of aryl chlorides with potassium ferrocyanide leading to aryl nitriles by using Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O as a highly efficient and recyclable catalytic system is described.[Figure not available: see fulltext.]
- Cai, Mingzhong,Huang, Bin,Liu, Rong,Xu, Caifeng
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- Water-Dispersible Pd–N-Heterocyclic Carbene Complex Immobilized on Magnetic Nanoparticles as a New Heterogeneous Catalyst for Fluoride-Free Hiyama, Suzuki–Miyaura and Cyanation Reactions in Aqueous Media
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Abstract: Pd–N-heterocyclic carbine complex immobilized on magnetic nanoparticles is synthesized and characterized by different techniques such as FT-IR, XPS, TEM, EDX, FESEM, VSM, TGA, and ICP. The synthesized catalyst was used as a new water dispersible heterogeneous catalyst in the fluoride-free Hiyama, Suzuki–Miyaura and cyanation reactions in pure water. By this method, different types of biaryls and aryl nitriles were synthesized in good to high yields by the reaction of a variety of aryl iodides, bromides and chlorides with triethoxyphenylsilane, phenylboronic acid and K4[Fe(CN)6]·3H2O, respectively. The presence of sulfonates as hydrophilic groups on the surface of the catalyst confers a highly water dispersible, active and yet magnetically recoverable Pd catalyst. The possibility to perform the reaction in water as a green medium, ease of the catalyst recovery and reuse by magnetic separation, and the absence of any additives or co-solvents make this method as an eco-friendly and economical protocol for the synthesis of biaryl derivatives and aryl nitriles. Graphic Abstract: A new water dispersible heterogeneous Pd–N-heterocyclic carbene for the efficient fluoride-free Hiyama, Suzuki–Miyaura and cyanation reactions in pure water is developed.[Figure not available: see fulltext.].
- Chahkamali, Farhad Omarzehi,Sansano, José Miguel,Sobhani, Sara
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- Zinc Oxide/Graphene Oxide as a Robust Active Catalyst for Direct Oxidative Synthesis of Nitriles from Alcohols in Water
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In this work, without using any linker or chemical modification of graphene oxide, a zinc oxide immobilized graphene oxide-based catalyst was used for the direct aerobic oxidative conversion of alcohols to the nitriles in water. In the first step, graphene oxide was prepared and then zinc ions were electrostatically adsorbed onto the surface of graphene oxide. In the following step, zinc oxide nanoparticles were generated via in-situ growth in presence of NaOH. It was illustrated that graphene oxide layers can control the size of in-situ generated zinc oxide nanoparticles. Various aromatic/aliphatic/heteroaromatic primary alcohols converted to the nitriles in high yields under O2 balloon with ZnO/GO catalyst. This catalyst can be used for 7 successful consecutive runs without significant loss of activity. Graphic Abstract: [Figure not available: see fulltext.]
- Sarvi, Iraj,Zahedi, Ehsan
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- Product selectivity controlled by manganese oxide crystals in catalytic ammoxidation
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The performances of heterogeneous catalysts can be effectively tuned by changing the catalyst structures. Here we report a controllable nitrile synthesis from alcohol ammoxidation, where the nitrile hydration side reaction could be efficiently prevented by changing the manganese oxide catalysts. α-Mn2O3 based catalysts are highly selective for nitrile synthesis, but MnO2-based catalysts including α, β, γ, and δ phases favour the amide production from tandem ammoxidation and hydration steps. Multiple structural, kinetic, and spectroscopic investigations reveal that water decomposition is hindered on α-Mn2O3, thus to switch off the nitrile hydration. In addition, the selectivity-control feature of manganese oxide catalysts is mainly related to their crystalline nature rather than oxide morphology, although the morphological issue is usually regarded as a crucial factor in many reactions.
- Hui, Yu,Luo, Qingsong,Qin, Yucai,Song, Lijuan,Wang, Hai,Wang, Liang,Xiao, Feng-Shou
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p. 2164 - 2172
(2021/09/20)
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- Selective oxidation of alcohols to nitriles with high-efficient Co-[Bmim]Br/C catalyst system
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An efficient method for catalyzing the ammoxidation of aromatic alcohols to aromatic nitriles was developed, in which a new heterogeneous catalyst based on transition metal elements was employed, the new catalyst was named Co-[Bmim]Br/C-700 and then characterized by X-ray photo-electronic spectroscopy, transmission electron microscope and X-ray diffraction. The reaction was carried out by two consecutive dehydrogenations under the catalysis of Co-[Bmim]Br/C-700, which catalytically oxidized the alcohol to the aldehyde, and then the aldehyde was subjected to ammoxidation to the nitrile. The catalyst system was suitable for a wide range of substrates and nitriles obtained in high yields, especially, the conversion rate of benzyl alcohol, 4-methoxybenzyl alcohol, 4-chlorobenzyl alcohol and 4-nitrobenzyl alcohol reached 100%. The substitution of ammonia and oxygen for toxic cyanide to participate in the reaction accords with the theory of green chemistry.
- Xia, Yu-Yan,Lv, Qing-Yang,Yuan, Hua,Wang, Jia-Yi
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p. 3957 - 3964
(2021/04/09)
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- Metal-Free Deoxygenation of Amine N-Oxides: Synthetic and Mechanistic Studies
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We report herein an unprecedented combination of light and P(III)/P(V) redox cycling for the efficient deoxygenation of aromatic amine N-oxides. Moreover, we discovered that a large variety of aliphatic amine N-oxides can easily be deoxygenated by using only phenylsilane. These practically simple approaches proceed well under metal-free conditions, tolerate many functionalities and are highly chemoselective. Combined experimental and computational studies enabled a deep understanding of factors controlling the reactivity of both aromatic and aliphatic amine N-oxides.
- Lecroq, William,Schleinitz, Jules,Billoue, Mallaury,Perfetto, Anna,Gaumont, Annie-Claude,Lalevée, Jacques,Ciofini, Ilaria,Grimaud, Laurence,Lakhdar, Sami
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p. 1237 - 1242
(2021/06/01)
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- Bis-morpholinophosphorylchloride, a novel reagent for the conversion of primary amides into nitriles
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Bis-morpholinophosphorylchloride (Bmpc), in the presence of a base, is an efficient dehydrating agent for both aromatic and aliphatic primary amides, and gives corresponding nitriles under mild conditions in god yields and purity. During the reaction the enantiomeric integrity remains intact.
- Rao, P. Purnachandra,Nowshuddin, Shaik,Jha, Anjali,Rao, B. Leela Maheswara,Divi, Murali K.,Rao
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supporting information
(2021/01/21)
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- Method for dehydrating primary amide into nitriles under catalysis of cobalt
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The invention provides a method for dehydrating primary amide into nitrile. The method comprises the following steps: mixing primary amide (II), silane, sodium triethylborohydride, aminopyridine imine tridentate nitrogen ligand cobalt complex (I) and a reaction solvent under the protection of inert gas, carrying out reacting at 60-100 DEG C for 6-24 hours, and post-treating reaction liquid to obtain a nitrile compound (III). According to the invention, an effective method for preparing nitrile compounds by cobalt-catalyzed primary amide dehydration reaction by using the novel aminopyridine imine tridentate nitrogen ligand cobalt complex catalyst is provided; and compared with existing methods, the method has the advantages of simple operation, mild reaction conditions, wide application range of reaction substrates, high selectivity, stable catalyst, high efficiency, and relatively high practical application value in synthesis.
- -
-
Paragraph 0126-0128
(2021/06/21)
-
- METHOD FOR PRODUCING NITRILE
-
The present invention provides a method of producing a nitrile from a primary amide, characterized in that the primary amide is subjected to a dehydration reaction in a supercritical fluid in the presence of an acid catalyst. The present invention achieves the object of reducing the corrosion of a reactor and the thermal decomposition of raw materials, as well as provides the effect of improving the reaction rate and nitrile selectivity.
- -
-
Paragraph 0080; 0090
(2021/02/05)
-
- Hydrosilylative reduction of primary amides to primary amines catalyzed by a terminal [Ni-OH] complex
-
A terminal [Ni-OH] complex1, supported by triflamide-functionalized NHC ligands, catalyzes the hydrosilylative reduction of a range of primary amides into primary amines in good to excellent yields under base-free conditions with key functional group tolerance. Catalyst1is also effective for the reduction of a variety of tertiary and secondary amides. In contrast to literature reports, the reactivity of1towards amide reduction follows an inverse trend,i.e., 1° amide > 3° amide > 2° amide. The reaction does not follow a usual dehydration pathway.
- Bera, Jitendra K.,Pandey, Pragati
-
supporting information
p. 9204 - 9207
(2021/09/20)
-
- Revisiting the synthesis of aryl nitriles: a pivotal role of CAN
-
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)
-
- An overview on the progress and development on the palladium catalyzed direct cyanation
-
Generation of the positive CN ion and the corresponding direct cyanation are both extremely important for cyanation of aromatic compounds. Hereby, we would like to report the simultaneous use of the new Pd nano-catalyst as well as the three types of the N-arylsulfonyl cyanamides (A, B and C) as potent reagents for the in situ generation of the positive CN ion for the direct cyanation of phenylboronic acids in acetonitrile at reflux conditions.
- Heydari, Somayyeh,Habibi, Davood,Reza Faraji, Ali,keypour, Hassan,Mahmoudabadi, Masoumeh
-
-
- Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species
-
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
-
-
- Method for converting aromatic aldehyde into aromatic nitrile by using sulfur powder promoted inorganic ammonium as nitrogen source (by machine translation)
-
The invention discloses a method for converting aromatic aldehyde into aromatic nitrile. The method is conversion of high yield of aromatic aldehyde one-pot reaction of sulfur powder promoted inorganic ammonium as a nitrogen source into aromatic nitrile. The method has the advantages of no need of metal participation, no need of strong oxide, compatibility of reaction to air, easiness in amplification to a gram scale and the like, and overcomes the problems of harsh reaction conditions, complex operation, low functional group compatibility and the like in the prior art. (by machine translation)
- -
-
Paragraph 0076; 0077
(2020/09/12)
-
- Chlorotropylium Promoted Conversions of Oximes to Amides and Nitriles
-
Chlorotropylium chloride as a catalyst for the transformations of oximes, ketones, and aldehydes to their corresponding amides and nitriles in excellent yields (up to 99 %) and in short reaction times (mostly 10–15 min). Oximes were electrophilically attacked on the hydroxyl oxygen by chlorotropylium. The produced tropylium oxime ethers were the key intermediates, of which the ketoxime ether led to amide through Beckmann rearrangement, and the aldoxime ether led to nitrile by nitrogen base DBU assisted formal dehydration. This chlorotropylium activation protocol offered general, mild, and efficient avenues bifurcately from oximes to both amides and nitriles by one organocatalyst.
- Xu, Jiaxi,Gao, Yu,Li, Zhenjiang,Liu, Jingjing,Guo, Tianfo,Zhang, Lei,Wang, Haixin,Zhang, Zhihao,Guo, Kai
-
p. 311 - 315
(2020/01/25)
-
- A Versatile VMPO Catalyst Prepared In Situ for Oxidative Ammonolysis of Isomeric Picolines and Xylenes
-
Abstract: The V2O5–MoO3–P2O5 (VMPO) catalyst has been prepared in situ by thermal decomposition of vanado-molybdophosphoric acid (PMoV) on TiO2 support at 475°C. The TiO2 supported VMPO catalysts are characterized by FT–IR, XRD, BET surface area, NH3–TPD, and H2–TPR. Morphology of the catalyst has been studied by TEM. The accumulated data indicate decomposition of PMoV and presence of phosphate and pyrophosphate phases of molybdenum and vanadium after calcination. TPD and TPR studies exhibit the moderate acidity and presence of V4+ in the material, respectively. The VMPO catalyst has been used for ammoxidation of six different compounds including three isomeric picolines and three isomeric xylenes to the corresponding nitriles with the yield of 90–96%.
- Dutta, P.,Pathak, D. D.,Senapati, Rabinarayan
-
p. 292 - 298
(2020/04/17)
-
- Atomically Dispersed Ru on Manganese Oxide Catalyst Boosts Oxidative Cyanation
-
There is a strong incentive for environmentally benign and sustainable production of organic nitriles to avoid the use of toxic cyanides. Here we report that manganese oxide nanorod-supported single-site Ru catalysts are active, selective, and stable for oxidative cyanation of various alcohols to give the corresponding nitriles with molecular oxygen and ammonia as the reactants. The very low amount of Ru (0.1 wt %) with atomic dispersion boosts the catalytic performance of manganese oxides. Experimental and theoretical results show how the Ru sites enhance the ammonia resistance of the catalyst, bolstering its performance in alcohol dehydrogenation and oxygen activation, the key steps in the oxidative cyanation. This investigation demonstrates the high efficiency of a single-site Ru catalyst for nitrile production.
- Gates, Bruce C.,Guan, Erjia,Meng, Xiangju,Wang, Chengtao,Wang, Hai,Wang, Liang,Wang, Sai,Xiao, Feng-Shou,Xu, Dongyang,Xu, Hua,Yang, Bo,Zhang, Jian
-
p. 6299 - 6308
(2020/07/21)
-
- Earth-Abundant Bimetallic Nanoparticle Catalysts for Aerobic Ammoxidation of Alcohols to Nitriles
-
Heterogeneous nitrogen-doped carbon-incarcerated iron/copper bimetallic nanoparticle (NP) catalysts prepared from nitrogen-containing polymers were developed. These catalysts showed activity higher than that of the corresponding monometallic NPs for aerobic ammoxidation of alcohols to nitriles. The important procedure for high activity in the catalyst preparation was found to be a simultaneous reduction of two metal salts.
- Kobayashi, Shu,Yang, Xi,Yasukawa, Tomohiro
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p. 7543 - 7548
(2020/06/27)
-
- An Efficient Synthesis of Nitriles from Aldoximes in the Presence of Trifluoromethanesulfonic Anhydride in Mild Conditions
-
Abstract: A new and convenient protocol has been proposed for the transformation of aldoximes to nitriles using trifluoromethanesulfonic anhydride and triethylamine. The proposed method allows a range of aldoximes, including aromatic, heterocyclic, aliphatic, and cycloaliphatic aldoximes, to be converted to the corresponding nitriles in good to excellent yields.
- Uludag, N.
-
p. 1640 - 1645
(2020/10/22)
-
- Metal-free dehydrosulfurization of thioamides to nitriles under visible light
-
A visible light-mediated, metal-free dehydrosulfurization reaction of thioamides to nitriles is described. This reaction features high yields, mild reaction conditions, and the use of a cheap organic dye as the photoredox catalyst and air as the oxidant.
- Xu, Tianxiao,Cao, Tianpeng,Feng, Qingyuan,Huang, Shenlin,Liao, Saihu
-
supporting information
p. 5151 - 5153
(2020/05/26)
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- NHC-catalyzed silylative dehydration of primary amides to nitriles at room temperature
-
Herein we report an abnormal N-heterocyclic carbene catalyzed dehydration of primary amides in the presence of a silane. This process bypasses the energy demanding 1,2-siloxane elimination step usually required for metal/silane catalyzed reactions. A detailed mechanistic cycle of this process has been proposed based on experimental evidence along with computational study.
- Ahmed, Jasimuddin,Hota, Pradip Kumar,Maji, Subir,Mandal, Swadhin K.,Rajendran, N. M.
-
supporting information
p. 575 - 578
(2020/01/29)
-
- Method for preparing aryl primary amide by adopting metal-catalyzed one-pot method
-
The invention discloses a method for synthesizing aryl primary amide by adopting a metal-catalyzed one-pot method. The method comprises the steps of: taking aryl bromidess as raw materials, allowing the aryl bromidess to react with a cyanide source under the action of a palladium catalyst, substituting bromine on an aromatic ring with cyano to obtain cyano aromatic hydrocarbon, directly adding anaqueous solution of alkali into the reaction solution without aftertreatment, and carrying out hydrolysis reaction to obtain aryl primary amide. Compared with the prior art, the method for preparing aryl primary amide from the aryl bromides has the advantages of the short synthesis route, fewer reaction steps, simple operation, mild conditions, the high conversion rate, low toxicity and industrialproduction potential.
- -
-
Paragraph 0029; 0030
(2020/04/06)
-
- Uniform silver nanoparticles on tunable porous N-doped carbon nanospheres for aerobic oxidative synthesis of aryl nitriles from benzylic alcohols
-
Tunable N-doped carbon nanospheres from sucrose as carbon source and Tris(2-aminoethyl)amine (TAEA) as nitrogen source by a simple and easily reproducible method were prepared. It was demonstrated that the tunable N-doping of carbon spheres could be realized by altering the ratio of TAEA in the raw materials. The content of doped nitrogen, surface area, pore volume and pore size of carbon nanospheres were increased with the increasing of TAEA amount in the hydrothermal process. Prepared N-doped carbon nanospheres act as solid ligand for anchoring of Ag NPs which generated via chemical reduction of Ag ions. Benzylic alcohols and aldehydes were converted into the aryl nitriles by using Ag/N-CS-1 nanospheres as the catalyst and O2 as the oxidant, efficiently. This catalyst was stable and could use for 6 successful runs.
- Hashemi, Alireza Nemati,Eshghi, Hossein,Lamei, Kamran
-
-
- Efficient cyanation of aryl halides with K4[Fe(CN)6] catalyzed by encapsulated palladium nanoparticles in biguanidine–chitosan matrix as core–shell recyclable heterogeneous nanocatalyst
-
Palladium nanoparticles encapsulated in biguanidine–functionalized chitosan matrix (Pd@CS–biguanidine) was applied as a reusable and core–shell nanocatalyst for cyanation of aryl iodides and bromides with K4[Fe(CN)6] as the cyanating agent. The nitriles were generated in good to excellent yield and the catalyst can be recycled and reapplied up to seven times with no significant change in its catalytic performance.
- Veisi, Hojat
-
p. 212 - 216
(2019/01/03)
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- Biosynthesis of Pd/MnO2 nanocomposite using Solanum melongena plant extract and its application for the one-pot synthesis of 5-substituted 1H-tetrazoles from aryl halides
-
In this work, for the first time, Solanum melongena plant extract was used for the green synthesis of Pd/MnO2 nanocomposite via reduction osf Pd(II) ions to Pd(0) and their immobilization on the surface of manganese dioxide (MnO2) nanoparticles (NPs) as an effective support. The synthesized nanocomposite were characterized by various analytical techniques such as Fourier transform infrared (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and UV–Vis spectroscopy. The catalytic activity of Pd/MnO2 nanocomposite was used as a heterogeneous catalyst for the one-pot synthesis of 5-substituted 1H-tetrazoles from aryl halides containing various electron-donating or electron-withdrawing groups in the presence of K4[Fe (CN)6] as non-toxic cyanide source and sodium azide. The products were obtained in good yields via a simple methodology and easy work-up. The nanocatalyst can be recycled and reused several times with no remarkable loss of activity.
- Nasrollahzadeh, Mahmoud,Ghorbannezhad, Fatemeh,Sajadi, S. Mohammad
-
-
- Enhanced catalytic activity of cobalt nanoparticles encapsulated with an N-doped porous carbon shell derived from hollow ZIF-8 for efficient synthesis of nitriles from primary alcohols in water
-
A cobalt catalyst derived from a unique core-shell structure based on hollow ZIF-8 and ZIF-67 (ZIF-67@ZIF-8) is prepared, which exhibits excellent catalytic efficiency for the synthesis of nitriles from alcohols in water under mild conditions (1 atm O2, 50 °C) owing to its large BET surface area, high pore volume, high basicity and hydrophilicity.
- Sun, Kang-Kang,Sun, Jia-Lin,Lu, Guo-Ping,Cai, Chun
-
supporting information
p. 4334 - 4340
(2019/08/21)
-
- Preparing method of aromatic nitrile or alkenyl nitrile compound
-
The invention discloses a preparing method of an aromatic nitrile or alkenyl nitrile compound. The preparing method comprises the following step that under protection of inert gas, an aryl or heteroaryl sulphonate compound shown in a formula II or an alkenyl sulphonate compound shown in a formula IV and a cyanation reagent are subjected to a cross-coupling reaction as is shown below in a solvent under the condition of the presence of a nickel complex, metal zinc and an additive to obtain the aromatic nitrile or alkenyl nitrile compound, wherein 4-dimethylamiopryidine (DMAP) is adopted as the additive, and zinc cyanide is adopted as the cyanation reagent. By means of the preparing method, cyanation of aryl sulphonate, heteroaryl sulphonate or alkenyl sulphonate can be simply and efficientlyachieved with a cheap catalysis system; moreover, the functional group compatibility and substrate universality are good, and a better application prospect and higher using value are provided for achieving industrial synthesis of the aromatic nitrile or alkenyl nitrile compound.
- -
-
Paragraph 0130-0132; 0169-0171; 0232-0233
(2019/10/01)
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- Primary amides to amines or nitriles: A dual role by a single catalyst
-
We report a manganese-catalyzed hydrosilylative reduction of various primary amides to amines (25 examples). On simple modification of the reaction conditions such as in the presence of a catalytic amount of secondary amide, the same catalyst can transform the primary amides into intermediate nitrile compounds (16 examples) in excellent yields. This is the first example where such a controlled catalytic transformation of primary amides to amines or nitriles with a single catalyst has been demonstrated.
- Das, Hari S.,Das, Shyamal,Dey, Kartick,Singh, Bhagat,Haridasan, Rahul,Das, Arpan,Ahmed, Jasimuddin,Mandal, Swadhin K.
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supporting information
p. 11868 - 11871
(2019/10/11)
-
- An Insight into Nitromethane as an Organic Nitrile Alternative Source towards the Synthesis of Aryl Nitriles
-
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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- Synthesis, characterization and catalytic performance of Pd(II) complex immobilized on Fe3O4@SiO2 nanoparticles for the ligand-free cyanation of aryl halides using K4Fe(CN)6
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This work shows the preparation of a novel magnetic catalyst via immobilization of Pd(II)-N-benzyl-N-(4-bromophenyl)-5-amino-1H-tetrazole complex on the Fe3O4@SiO2 nanoparticles (NPs). The application of Fe3O4@SiO2 NPs supported Pd(II)-N-benzyl-N-(4-bromophenyl)-5-amino-1H-tetrazole complex [Fe3O4@SiO2-BAT-Pd(II)] nanocatalyst is described for the cyanation of aryl iodides and bromides to the corresponding aryl nitriles using potassium hexacyanoferrate(II) [K4Fe(CN)6] as a non-toxic and economic cyanating agent under ligand- and additive-free conditions. Some aryl nitriles were efficiently synthesized from the corresponding aryl bromides and iodides in the presence of Fe3O4@SiO2-BAT-Pd(II) nanocomplex. The core-shell nanocomplex demonstrated the superior catalytic performance for the synthesis of synthetically valuable aryl nitriles within good to excellent yields. This process eliminates the need to handle highly toxic metal cyanides, and it can be easily recovered and reused for six consecutive runs with no decreasing of its catalytic capability. Highlights: Preparation of Pd(II) complex immobilized on Fe3O4@SiO2 nanoparticles [Fe3O4@SiO2-BAT-Pd(II) nanocomplex]. Characterization of Fe3O4@SiO2-BAT-Pd(II) nanocomplex using XRD, FT-IR, EDS, VSM, TEM and FESEM analyses. Catalytic cyanation of the various aryl halides with K4Fe(CN)6 under ligand-free conditions. The nanocomplex can be recovered and isolated six times with no significant loss of its catalytic ability.
- Nasrollahzadeh, Mahmoud,Maryami, Mahboobe,Sajjadi, Mohaddeseh,Mehdipour, Ebrahim
-
-
- Selective aerobic oxidation of benzylic amines to aryl nitriles catalyzed by CuBr2/N-methyl imidazole
-
A convenient and efficient copper-catalyzed aerobic oxidation of primary amines to aryl nitriles was described. Various benzylic and allylic amines were selectively oxidized to the corresponding nitriles in high yields using CuBr2/NMI as the catalyst and O2 as the oxidant. The oxidation reaction profiles monitored by 1H NMR disclosed the scenario of the reaction path as well as the role of the additives. The addition of NMI increased the rate of reaction and suppressed the hydrolysis and the deamination.
- Shen, Yifan,Zhou, Yu,Jiang, Lili,Ding, Guangni,Luo, Luo,Zhang, Zhaoguo,Xie, Xiaomin
-
p. 4266 - 4271
(2018/07/06)
-
- Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides
-
The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized molecules is of fundamental interest because nitrogen-containing motifs are found in a large number of life science molecules, natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein we report the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O2 or air. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesise functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Additionally, applying this iron-based protocol, primary amides have also been prepared in a water medium.
- Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Sharif, Muhammad,Kalevaru, Narayana V.,Jagadeesh, Rajenahally V.
-
supporting information
p. 266 - 273
(2018/01/12)
-
- Optimization of method for synthesizing 3-cyanopyridine by 3-picoline
-
The invention relates to a technical field of organic synthesis, in particular to optimization of a method for synthesizing 3-cyanopyridine by 3-picoline. According to a design, a catalyst is preparedby an impregnation method by taking activated carbon as
- -
-
Paragraph 0018-0033
(2020/10/06)
-
- Corresponding amine nitrile and method of manufacturing thereof
-
The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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-
- Catalytic Promiscuity of Galactose Oxidase: A Mild Synthesis of Nitriles from Alcohols, Air, and Ammonia
-
We report an unprecedented catalytically promiscuous activity of the copper-dependent enzyme galactose oxidase. The enzyme catalyses the one-pot conversion of alcohols into the related nitriles under mild reaction conditions in ammonium buffer, consuming ammonia as the source of nitrogen and dioxygen (from air at atmospheric pressure) as the only oxidant. Thus, this green method does not require either cyanide salts, toxic metals, or undesired oxidants in stoichiometric amounts. The substrate scope of the reaction includes benzyl and cinnamyl alcohols as well as 4- and 3-pyridylmethanol, giving access to valuable chemical compounds. The oxidation proceeds through oxidation from alcohol to aldehyde, in situ imine formation, and final direct oxidation to nitrile.
- Vilím, Jan,Knaus, Tanja,Mutti, Francesco G.
-
supporting information
p. 14240 - 14244
(2018/10/15)
-
- In situ immobilized palladium nanoparticles on surface of poly-methyldopa coated-magnetic nanoparticles (Fe3O4@PMDA/Pd): A magnetically recyclable nanocatalyst for cyanation of aryl halides with K4[Fe(CN)6]
-
Poly-methyldopa (PMDP)-coated Fe3O4 nanoparticles (Fe3O4@PMDP) have been synthesized through a simple and green procedure. In the present study, for the first time, Pd nanoparticles were successfully deposited using Fe3O4@PMDP as a core-shell magnetic coordinator and stabilizer agent. In this protocol, Pd ions were adsorbed on surfaces of Fe3O4@PMDP through immersion of the PMDP-coated Fe3O4 nanoparticles into a palladium plating bath. Next, they were reduced in situ to palladium nanoparticles using PMDP's N-containing groups and reducing ability. The structure, morphology and physicochemical properties of the synthesized nanoparticles were characterized by different analytical techniques such as energy-dispersive X-ray spectroscopy (EDS), field emission scanning electron microscope (FESEM), Fourier-transform infrared spectroscopy (FT-IR) spectroscopy, high resolution transmission electron microscopy (HR-TEM), inductively coupled plasma (ICP), thermo gravimetric analysis (TGA), vibrating sample magnetometer (VSM), and X-ray photoelectron spectroscopy (XPS). Core-shell Fe3O4@PMDP/Pd(0) nanoparticles showed excellent catalytic performance as a reusable nanocatalyst for cyanation of aryl iodides and bromides with K4[Fe(CN)6] as the cyanating agent. The nitriles were obtained in good to excellent yield and the catalyst can be recycled and reapplied up to seven times with only very slight decrease in its catalytic performance.
- Veisi, Hojat,Hemmati, Saba,Safarimehr, Parisa
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p. 204 - 212
(2018/07/25)
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- Pd-Catalyzed Cyanation of (Hetero)Aryl Halides by Using Biphosphine Ligands
-
Tetraadamantylbiphosphine (TABP; L1), which showed superior activity in the palladium-catalyzed cyanation of 4-chloroanisole compared to standard phosphines, was synthesized as a new ligand. The generality of the new catalytic system was shown by the cyanation reaction of approximately 30 (hetero)aryl halides including hindered, electron-rich, and electron-poor aryl chlorides. These reactions constitute the first examples of using biphosphine ligands in Pd-catalyzed coupling reactions.
- Zhang, Shaoke,Neumann, Helfried,Beller, Matthias
-
supporting information
p. 67 - 70
(2017/11/27)
-
- Magnetically recoverable lanthanum hydroxide as an efficient catalyst for Aerobic Oxidative Conversions of primary alcohols to the nitriles
-
Herein we report a novel magnetically recoverable lanthanum hydroxide nanoparticles for oxidative synthesis of nitriles directly from corresponding alcohols with ammonia as nitrogen source. The procedure for the preparation and characterization of La(OH)3/Fe3O4 magnetic nanoparticles were investigated and the scope and generality of the method was explored for a series of structurally diverse primary alcohols with electron-donating and electron-withdrawing groups. The best result was observed when 5?mol% of La with respect to the benzyl alcohol was used at reflux condition under O2 atmosphere. The La(OH)3/Fe3O4 magnetic nanoparticles could be easily isolated from the reaction mixture with an external magnet and reused at least 5 times without significant loss in activity.
- Ziaee, Fariborz,Gholizadeh, Mostafa,Seyedi, Seyed Mohammad
-
-
- NH3?H2O: The Simplest Nitrogen-Containing Ligand for Selective Aerobic Alcohol Oxidation to Aldehydes or Nitriles in Neat Water
-
Aqueous ammonia (NH3?H2O) has been shown to serve as the simplest nitrogen-containing ligand to effectively promote copper-catalyzed selective alcohol oxidation under air in water. A series of alcohols with varying electronic and steric properties were selectively oxidized to aldehydes with up to 95 % yield. Notably, by increasing the amount of aqueous ammonia in neat water, the exclusive formation of aryl nitriles was also accomplished with good-to-excellent yields. Additionally, the catalytic system exhibits a high level of functional group tolerance with ?OH, ?NO2, esters, and heteroaryl groups all being amenable to the reaction conditions. This one-pot and green oxidation protocol provides an important synthetic route for the selective preparation of either aldehydes or nitriles from commercially available alcohols.
- Zhang, Guofu,Ma, Danting,Zhao, Yiyong,Zhang, Guihua,Mei, Guangyao,Lyu, Jinghui,Ding, Chengrong,Shan, Shang
-
p. 885 - 889
(2018/12/10)
-
- Practical CuCl/DABCO/4-HO-TEMPO-catalyzed oxidative synthesis of nitriles from alcohols with air as oxidant
-
A mild and efficient methodology for the direct oxidative synthesis of nitriles from easily available alcohols and aqueous ammonia by employing CuCl/DABCO/4-HO-TEMPO as the catalysts is described. This protocol uses the air as a green oxidant and aqueous ammonia as the nitrogen source at room temperature. A variety of aryl, heterocyclic and allylic alcohols are smoothly converted into the corresponding nitriles in good to excellent yields.
- Hu, Yongke,Chen, Lei,Li, Bindong
-
supporting information
p. 464 - 466
(2017/11/13)
-
- Dehydration of Amides to Nitriles under Conditions of a Catalytic Appel Reaction
-
A highly expedient protocol for a catalytic Appel-type dehydration of amides to nitriles has been developed that employs oxalyl chloride and triethylamine along with triphenylphosphine oxide as a catalyst. The reactions are usually complete in less than 10 min with only a 1 mol % catalyst loading. The reaction scope includes aromatic, heteroaromatic, and aliphatic amides, including derivatives of α-hydroxy and α-amino acids.
- Shipilovskikh, Sergei A.,Vaganov, Vladimir Yu.,Denisova, Elena I.,Rubtsov, Aleksandr E.,Malkov, Andrei V.
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supporting information
p. 728 - 731
(2018/02/09)
-
- Synthesis of Nitriles from Primary Amides or Aldoximes under Conditions of a Catalytic Swern Oxidation
-
The preparation of nitriles from primary amides or aldoximes was achieved by using oxalyl chloride with a catalytic amount of dimethyl sulfoxide in the presence of Et3N. The reactions were complete within 1 h after addition at room temperature. A diverse range of cyano compounds were obtained in good to excellent yields, including aromatic, heteroaromatic, cyclic, and acyclic aliphatic species.
- Ding, Rui,Liu, Yongguo,Han, Mengru,Jiao, Wenyi,Li, Jiaqi,Tian, Hongyu,Sun, Baoguo
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p. 12939 - 12944
(2018/10/20)
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- Intramolecular alkene hydroamination and degradation of amidines: Divergent behavior of rare earth metal amidinate intermediates
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Direct N-H addition of amidines to alkenes is a highly valuable but challenging transformation that remains elusive. Now, the intramolecular hydroamidination of N-alkenylamidines is achieved by using a rare earth catalyst, which provides an efficient and atom-economical approach for substituted imidazolines and tetrahydropyrimidines. Moreover, a mild and efficient method for the catalytic degradation of amidines to give amines and nitriles is also developed. Additionally, amidine reconstruction followed by an intramolecular alkene hydroamidination strategy for the synthesis of substituted imidazolines and tetrahydropyrimidines from secondary enamines and inactive amidines has also been established, which may circumvent the need for some unavailable starting materials. The mechanistic studies prove that these reactions proceed via a key lanthanide amidinate intermediate that can undergo substrate- and amine-controlled chemodivergent transformations: intramolecular alkene insertion, nitrile extrusion, amidinate reconstruction, or a combination of the reactions. The results presented here not only demonstrate the synthetic potential and versatility of alkene hydroamidination with substrates, but also provide a good insight into the factors that promote or deter the hydroamidination of alkenes.
- Zhang, Dexing,Liu, Ruiting,Zhou, Xigeng
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p. 5573 - 5581
(2018/11/20)
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- Nickel-Catalyzed Cyanation of Phenol Derivatives with Zn(CN)2 Involving C-O Bond Cleavage
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An efficient nickel-catalyzed cyanation of aryl sulfonates, fluorosulfonates, and sulfamates with Zn(CN)2 was developed, which provides a facile access to the nitrile products in generally good to excellent yields. The reaction is accomplished by using NiII complex as the precatalyst and DMAP as the additive. The method also displays wide functional group compatibility; for example, keto, methoxy, N,N-dimethylamino, cyano, ester, and pyridyl groups are well-tolerated during the reaction process.
- Gan, Yi,Wang, Gaonan,Xie, Xin,Liu, Yuanhong
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p. 14036 - 14048
(2018/11/03)
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- An efficient protocol for the production of pymetrozine via a new synthetic strategy
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A practical four-step synthesis of pymetrozine is reported, starting from a green chemical dimethyl carbonate and using the key intermediate methyl (E)-1-(2-oxopropyl)-2-(pyridin-3-ylmethylene)hydrazine-1-carboxylate. The main advantages of the route include inexpensive starting materials, environmental friendliness, short synthetic route, easy-to-use synthetic method and acceptable overall yield. A scale-up experiment was carried out to provide pymetrozine with 99.84% purity in 53.2% total yield.
- Zhou, Qifan,Du, Fangyu,Shi, Yajie,Liu, Wenqiang,Liu, Dongdong,Chen, Guoliang
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p. 434 - 438
(2018/09/12)
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- Nickel-catalyzed cyanation of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine
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A nickel-catalyzed cyanation of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine (TCT) using aminoacetonitrile as the cyanating agent is described. This catalytic system delivered the desired products in moderate to good yields with good substrate compatibility. The readily available starting materials, cost-effective nickel catalyst and metal-free cyanating agent are the major features of the present method.
- Wang, Liang,Wang, Yaoyao,Shen, Jun,Chen, Qun,He, Ming-Yang
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supporting information
p. 4816 - 4820
(2018/07/13)
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- Nickel-Catalyzed Deoxycyanation of Activated Phenols via Cyanurate Intermediates with Zn(CN)2: A Route to Aryl Nitriles
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A novel, and efficient nickel-catalyzed deoxycyanation of phenolic compounds using relatively nontoxic Zn(CN)2 as the cyanide source was developed. The reaction of C-O bond activated phenolic compounds by 2,4,6-trichloro-1,3,5-triazine with Zn(CN)2 in the presence of a nickel precatalyst afforded the aromatic nitriles in good to excellent yields.
- Heravi, Majid M.,Panahi, Farhad,Iranpoor, Nasser
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supporting information
p. 2753 - 2756
(2018/05/22)
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- Merging visible-light photoredox and copper catalysis in catalytic aerobic oxidation of amines to nitriles
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Visible-light-initiated homogeneous oxidative synthesis of nitriles from amines was accomplished through a combined use of photoredox and copper catalysis. This transformation was performed at room temperature with O2 as the oxidant.
- Tao, Chuanzhou,Wang, Bin,Sun, Lei,Liu, Zhou,Zhai, Yadong,Zhang, Xiulian,Wang, Jian
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supporting information
p. 328 - 332
(2017/01/13)
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