- Atomically Dispersed Ru on Manganese Oxide Catalyst Boosts Oxidative Cyanation
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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
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p. 6299 - 6308
(2020/07/21)
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- Cascade Process for Direct Transformation of Aldehydes (RCHO) to Nitriles (RCN) Using Inorganic Reagents NH2OH/Na2CO3/SO2F2 in DMSO
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A simple, mild, and practical process for direct conversion of aldehydes to nitriles was developed feathering a wide substrate scope and great functional group tolerability (52 examples, over 90% yield in most cases) using inorganic reagents (NH2OH/Na2CO3/SO2F2) in DMSO. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable nitriles in a pot, atom, and step-economical manner without transition metals. This protocol will serve as a robust tool for the installation of cyano-moieties to complicated molecules.
- Fang, Wan-Yin,Qin, Hua-Li
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p. 5803 - 5812
(2019/05/14)
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- Ullmann diaryl ether synthesis catalyzed by copper (I)/pyridine-functionalized silane
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Ullmann-type diaryl ether synthesis was performed under mild conditions in DMF/K2CO3using a pyridinefunctionalized silane as a ligand. The productswere obtained in good yields. This method tolerates a variety of functional groups and is effective in the synthesis of hindered diaryl ethers and heteroaryl ethers.
- Zhang, Baohua,Shi, Lanxiang,Guo, Ruixia,Liu, Sijie
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p. 930 - 932
(2016/07/06)
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- Copper-catalyzed synthesis of nitriles by aerobic oxidative reaction of alcohols and ammonium formate
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An efficient methodology has been developed for the synthesis of nitriles through an aerobic oxidative reaction of alcohols and ammonium formate with copper as a homogeneous catalyst under a normal air atmosphere and solvent-free conditions. This protocol uses the air as a green oxidant and ammonium formate as the nitrogen source. A wide range of substrates were well tolerated in the reaction that gave water as a byproduct. A facile protocol, which uses copper as an effective homogeneous catalyst, has been developed for the oxidative synthesis of nitriles from alcohols and ammonium formate. This system uses air as a green oxidant and produces water as an environmentally benign side product. Copyright
- Yadav, Dilip Kumar T.,Bhanage, Bhalchandra M.
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p. 5106 - 5110
(2013/11/06)
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- A novel oxidative transformation of alcohols to nitriles: An efficient utility of azides as a nitrogen source
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An efficient methodology to oxidize benzylic and cinnamyl alcohols to their corresponding nitriles in excellent yields has been developed. This methodology employs DDQ as an oxidant and TMSN3 as a source of nitrogen in the presence of a catalytic amount of Cu(ClO4)2·6H 2O.
- Rokade, Balaji V.,Malekar, Sanjeev K.,Prabhu, Kandikere Ramaiah
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supporting information; experimental part
p. 5506 - 5508
(2012/07/03)
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- Metal-free arylation of oxygen nucleophiles with diaryliodonium salts
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Phenols and carboxylic acids are efficiently arylated with diaryliodonium salts. The reaction conditions are mild, metal free, and avoid the use of halogenated solvents, additives, and excess reagents. The products are obtained in good-to-excellent yields after short reaction times. Steric hindrance is very well tolerated, both in the nucleophile and diaryliodonium salt. The scope includes ortho- and halo-substituted products, which are difficult to obtain by metal-catalyzed protocols. Many functional groups are tolerated, including carbonyl groups, heteroatoms, and alkenes. Unsymmetric salts can be chemoselectively utilized to obtain products with hitherto unreported levels of steric congestion. The arylation has been extended to sulfonic acids, which can be converted to sulfonate esters by two different approaches. With recent advances in efficient synthetic procedures for diaryliodonium salts the reagents are now inexpensive and readily available. The iodoarene byproduct formed from the iodonium reagent can be recovered quantitatively and used to regenerate the diaryliodonium salt, which improves the atom economy. Copyright
- Jalalian, Nazli,Petersen, Tue B.,Olofsson, Berit
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supporting information
p. 14140 - 14149,10
(2012/12/12)
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- Chemoselective Schmidt reaction mediated by triflic acid: Selective synthesis of nitriles from aldehydes
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An excellent utility of Schmidt reaction of aldehydes to access corresponding nitriles in an instantaneous reaction is demonstrated. The reaction of aldehydes with NaN3 and TfOH furnishes the corresponding nitriles in near quantitative yields and tolerates a variety of electron-withdrawing and electron-donating substituents on the substrates. Formanilides, a common side product in Schmidt reaction, is not observed in this reaction. Besides these advantages, the salient feature of this reaction is that it exhibits a remarkable chemoselectivity, as acid and ketone functionalities are well tolerated under the reaction conditions. The reaction is easily scalable, high yielding, and nearly instantaneous.
- Rokade, Balaji V.,Prabhu, Kandikere Ramaiah
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experimental part
p. 5364 - 5370
(2012/09/07)
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- Room temperature, metal-free synthesis of diaryl ethers with use of diaryliodonium salts
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A fast, high-yielding synthesis of diaryl ethers with use of mild and metal-free conditions has been developed. The scope includes bulky ortho-substituted diaryl ethers, which are difficult to obtain by metal-catalyzed protocols. Halo-substituents, racemization-prone amino acid derivatives, and heteroaromatics are also tolerated. The methodology is expected to be of high utility in the synthesis of complex molecules and in the pharmaceutical industry.
- Jalalian, Nazli,Ishikawa, Eloisa E.,Silva, Luiz F.,Olofsson, Berit
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supporting information; experimental part
p. 1552 - 1555
(2011/04/26)
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- CuI nanoparticles for C-N and C-O cross coupling of heterocyclic amines and phenols with chlorobenzenes
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(Chemical Equation Presented) Employing CuI nanoparticles as an efficient catalyst for the cross-coupling reactions of various N/O nucleophilic reagents with aryl chlorides could be successfully carried out under mild conditions in the absence of both the ligands and strong bases. A variety of products including N-arylimidazoles and aryl ethers were synthesized in good to excellent yields. 2009 American Chemical Society.
- Sreedhar,Arundhathi,Reddy, P. Linga,Kantam, M. Lakshmi
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supporting information; experimental part
p. 7951 - 7954
(2010/01/16)
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- An efficient Ullmann-type C-O bond formation catalyzed by an air-stable copper(I)-bipyridyl complex
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(Chemical Equation Presented) An efficient O-arylation of phenols and aliphatic alcohols with aryl halides was developed that uses an air-stable copper(I) complex as the catalyst. This arylation reaction can be performed in good yield in the absence of Cs2CO3. A variety of functional groups are compatible with these reaction conditions with low catalyst loading levels.
- Niu, Jiajia,Zhou, Hua,Li, Zhigang,Xu, Jingwei,Hu, Shaojing
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p. 7814 - 7817
(2008/12/22)
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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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p. 137 - 140
(2007/10/03)
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- Design and synthesis of low molecular weight compounds with complement inhibition activity
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An attempt was made to synthesize a series of non-cytotoxic low molecular weight compounds of varying substitutions and functionalities having pharmacophore activity like carbonyl compounds, carboxylic acid and bioisosteres like tetrazole and phenyl acrylic acid. The in vitro assay of these analogues for the inhibition of complement activity revealed significant inhibitory activity for varying substituents and, particularly, for bioisosteres, that is, tetrazole and phenyl acrylic acid derivatives.
- Master, Hoshang E.,Khan, Shabana I.,Poojari, Krishna A.
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p. 4891 - 4899
(2007/10/03)
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- Design, synthesis and evaluation of potential inhibitors of HIV gp120-CD4 interactions
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This paper describes an approach to prevent HIV-cell fusion by disrupting the interaction between HIV protein gp120 and CD4 receptor. The CD4 residues Phe43 and Arg59 make important interactions with gp120. Small molecule analogues were made to mimic the crucial features of these residues. The analogues were assayed using a cellular 'FIGS' assay to measure inhibition of cell fusion and caused some inhibition.
- Boussard, Cyrille,Klimkait, Thomas,Mahmood, Naheed,Pritchard, Martin,Gilbert, Ian H.
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p. 2673 - 2676
(2007/10/03)
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- Synthesis of low molecular weight compounds with complement inhibition activity
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An attempt was made to synthesize a series of non-cytotoxic low molecular weight meta-substituted aromatic ethers (2-4, 5-7) and some of their bioisosteres (14-16) and to evaluate their activity on the activation of human complement (classical pathway) and their intrinsic hemolytic activity. The in vitro assay results of the inhibition of complement-mediated hemolysis by these analogues indicate that the aldehydic meta substituted aromatic ethers show inhibitory potency, while carboxylic acid meta substituted aromatic ethers show hemolytic activity. Some of the bioisosteres exhibit both inhibitory as well as hemolytic property.
- Master, Hoshang E.,Khan, Shabana I.,Poojari, Krishna A.
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p. 1249 - 1251
(2007/10/03)
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- Improved efficient conversion of aldehydes to nitriles via their N,N- dimethyl hydrazones
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Aldehyde N,N-dimethylhydrazones undergoes facile oxidative cleavage to nitriles on reaction with DMS and K2CO3 in quantitative yields. Nitriles can also be easily obtained in high yields in a 'one-pot' process starting from the corresponding aldehydes.
- Kamal, Ahmed,Arifuddin,Venugopal Rao
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p. 4507 - 4512
(2007/10/03)
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- Tris(polyoxaalkyl)amines (Trident), a New Class of Solid-Liquid Phase-Transfer Catalysts
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A new class of solid-liquid phase-transfer catalysts has been prepared.These tris(polyoxaalkyl)amines (I) are designed to obtain the best balance between straightforward synthesis (cheap starting materials), high activity, easy recovery, and low toxicity.The catalysts are synthesized from ethylene glycols by a simple one-step method in yields in the range of 65-81percent.They show high catalytic effects in aliphatic nucleophic substitutions and aromatic nucleophilic substitutions on activated and unactivated molecules.In the Ullman synthesis (a new PTC reaction) there is a synergic effect of anionic activation by tridents and by copper salts.Reactions have been carried out at temperatures up to 180 deg C without evidence of decomposition of the tris(polyoxaalkyl)amines. The behavior and catalytic activity of these catalysts are discussed.
- Soula, Gerard
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p. 3717 - 3721
(2007/10/02)
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- Polar Radicals. 17. On the Mechanism of Iodine Atom Transfer. A 9-I-2 Intermediate
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The atom-transfer reaction of iodine from an aryl iodide to a phenyl radical has been shown to proceed via a 9-I-2 ntermediate.The relative kinetics of the reactions of the intermediate were investigated by studying its mode of decomposition upon formation from the reduction of a series of unsymmetrically substituted diaryliodonium salts.The iodonium salts were reduced by the electron-transfer reactions with several reagents: di-tert-butyl nitroxide, sodium 2,6-di-tert-butylphenylate, and sodium phenylate.The reduction by electron transfer of the iodonium salts by the latter reaction gives high yields of diaryl ethers.The mechanism fo ether formation has been shown to proceed by two mechanistic pathways.For the diaryliodonium salts that have a p-cyano or p-nitro substituent, the ether is formed by a nucleophilic aromatic substitution; however, when the substituents were not strongly electron withdrawing, the mechanism resulting in ether formation involved electron transfer from the phenylate anion to the iodonium salt to form the phenoxy radical and a 9-I-2 intermediate.The intermediate decomposes to an aryl radical and an aryl iodide.The ether is formed from the efficient coupling of the aryl radical and the phenoxy radical.
- Tanner, Dennis D.,Reed, Darwin W.,Setiloane, B.P.
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p. 3917 - 3923
(2007/10/02)
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- Ullmann reaction for the synthesis of diaryl ethers
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The Ullman reaction for the preparation of diaryl ethers by coupling aryl halides with metal phenolates is conducted in the presence of at least one tertiary amine sequestering agent having the formula:
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