- Selective aerobic hydrolysis of nitriles to amides using cobalt(II)/zinc
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A novel protocol has been developed for the aerobic hydrolysis of nitriles to amides using cobalt(II)/zinc without using any strong acids and bases under solvent-free conditions. The reaction showed good performance for benzonitriles with sensitive groups such as ester and carboxylic acid.
- Keshipour, Sajjad,Shaabani, Ahmad
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- Highly active, chemo- and enantioselective Pt-SPO catalytic systems for the synthesis of aromatic carboxamides
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Platinum complexes modified with a chiral non-racemizing SPO preligand 1 have been applied in the hydration of aromatic nitriles. [Pt(1)3Cl]Cl formed readily from Pt(COD)Cl2. The chiral secondary phosphine oxide complex showed moderate activity in the hydration of para- and meta-substituted benzonitriles, but failed in converting the ortho-substituted derivatives. The hydride complex PtH(PR2OH)(PR2O-H?OR2P) (PR2OH = 1) formed from Pt(PPh3)4 and 1, and the cationic complex derived from [Pt(1)3Cl]Cl via direct chloride abstraction with AgNO3 were proven to be considerably more active, allowing us to extend the scope to the hydration of ortho-substituted aromatic nitriles, including axially chiral [1,1′-binaphthalene]-2,2′-dicarbonitrile. In the hydration of the racemic dinitrile, successful kinetic resolution has been achieved. The catalysts derived from non-racemizing 1 are the first chiral transition metal-SPO complexes that provide kinetic resolution in the hydration of a racemic chiral nitrile.
- Gulyás, Henrik,Rivilla, Ivan,Curreli, Simona,Freixa, Zoraida,Van Leeuwen, Piet W. N. M.
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- Light-induced hydrolysis of nitriles by photoproduced α-MnO 2 nanorods on polystyrene beads
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A green chemistry approach has been furnished for photochemical deposition of α-MnO2 nanorods onto the surface of functionalized polystyrene beads through immobilization of MnO+4- in alkaline condition under visible light. Then the composite material was exploited as a fruitful and novel solid-phase catalyst for the one-step and facile synthesis of amide compounds from nitriles under visible light in weakly basic medium.
- Jana, Subhra,Praharaj, Snigdhamayee,Panigrahi, Sudipa,Basu, Soumen,Pande, Surojit,Chang, Chien-Hsiang,Pal, Tarasankar
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- Simple and efficient cleavage of the N-(1-phenylethyl) unit of carboxamides with methanesulfonic acid
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Cleavage of the N-(1-phenylethyl) unit of carboxamides using less than 1 equiv of MsOH in refluxing toluene was found to be simple and very efficient leading to the desired amides in good to excellent yields, and also proved to be more effective compared with reductive methods using hydrogen sources, or acid hydrolysis reagents such as TFA and TsOH. The method selectively cleaved only the N-(1-phenylethyl) group of N-benzyl-N-(1-phenylethyl)amides.
- Paik, Seunguk,Lee, Jun Young
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- Choline chloride based eutectic solvent: An efficient and reusable solvent system for the synthesis of primary amides from aldehydes and from nitriles
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Choline chloride: a 2ZnCl2 based deep eutectic solvent was found to be a simple, green, efficient and new solvent system for the preparation of primary amides from aldehydes. The same catalytic system is also applicable for the preparation of amides from nitriles. Good to excellent yields of primary amides were obtained in both these transformations.
- Patil, Umakant B.,Singh, Abhilash S.,Nagarkar, Jayashree M.
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- Transition metal-free sodium borohydride promoted controlled hydration of nitriles to amides
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A transition metal-free process, promoted by sodium borohydride, has been developed for convenient and selective hydration of nitriles to corresponding amides. The present process converts the aromatic, aliphatic, and heteroaromatic nitriles with wide functional group tolerance. The regioselective hydration of one nitrile moiety in the presence of an other nitrile group makes high impact in the present protocol.
- Verma, Praveen Kumar,Kumar, Neeraj,Sharma, Upendra,Bala, Manju,Kumar, Vishal,Singh, Bikram
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- Visible Light-Induced Iodine-Catalyzed Transformation of Terminal Alkynes to Primary Amides via C≡C Bond Cleavage under Aqueous Conditions
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The visible light-induced iodine-catalyzed oxidative cleavage of the C≡C bond for transforming terminal alkynes into primary amides in the presence of ammonia under aqueous conditions is described. This metal-free protocol which ensued via initial hydroamination of the acetylene bond followed by liberation of diiodomethane (CH2I2) was found to be applicable to aromatic, heteroaromatic and aliphatic alkynes.
- Dighe, Shashikant U.,Batra, Sanjay
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- Catalytic Hydration of Nitriles to Amides with Manganese Dioxide on Silica Gel
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Hydration of representative nitriles with silica gel supported manganese dioxide at the reflux temperature of hydrocarbon solvents gives the corresponding amides in good to excellent yield.Phenylacetonitrile, however, was partially oxidized to benzoylformamide.Other manganese catalyst systems were also evaluated.
- Liu, Kwang-Ting,Shih, Mei-Hsiu,Huang, Hsiau-Wen,Hu, Chia-Juei
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- Trash to treasure: Eco-friendly and practical synthesis of amides by nitriles hydrolysis in WepPA
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The hydration of nitriles to amides in a water extract of pomelo peel ash (WEPPA) was realized with moderate to excellent yields without using external transition metals, bases or organic solvents. This reaction features a broad substrate scope, wide functional group tolerance, prominent chemoselectivity, and good reusability. Notably, a magnification experiment in this bio-based solvent at 100 mmol further demonstrated its practicability.
- Sun, Yajun,Jin, Weiwei,Liu, Chenjiang
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- Selective hydration of nitriles to amides promoted by an Os-NHC catalyst: Formation and X-ray characterization of κ2-amidate intermediates
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The complex [Os(η6-p-cymene)(OH)IPr]OTf (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf = CF3SO 3) reacts with benzonitrile and acetonitrile to afford the κ2-amidate derivatives [Os(η6-p-cymene) {κ2O,N-NHC(O)R}IPr]OTf (R = Ph (2), CH3 (3)). Their formation has been investigated by DFT calculations (B3PWP1), starting from the model intermediate [Os(η6-benzene)(OH)(CH3CN)IMe] + (IMe = 1,3-bis(2,6-dimethylphenyl)imidazolylidene). Complex 2 has been characterized by X-ray diffraction analysis. In the presence of water, the κ2-amidate species release the corresponding amides and regenerate 1. In agreement with this, complex 1 has been found to be an efficient catalyst for the selective hydration of a wide range of aromatic and aliphatic nitriles to amides, including substituted benzonitriles, cyanopyridines, acetonitrile, and 2-(4-isobutylphenyl)propionitrile among others. The mechanism of the catalysis is also discussed.
- Buil, Maria L.,Cadierno, Victorio,Esteruelas, Miguel A.,Gimeno, Jose,Herrero, Juana,Izquierdo, Susana,Onate, Enrique
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- Potassium trimethylsilanolate mediated hydrolysis of nitriles to primary amides
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Treatment of nitriles with potassium trimethylsilanolate under mild anhydrous conditions readily yields the corresponding primary amides after a simple aqueous workup. (C) 2000 Elsevier Science Ltd.
- Merchant, Kevin J.
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- Efficient Mo(VI)-catalyzed hydration of nitrile with acetaldoxime
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A method for the selective hydration of nitrile to amide by employing commercially available acetaldoxime and inexpensive oxometallate such as molybdate, vanadate, and tungstate in environmentally friendly water is described. Under this protocol, nitriles including aromatic nitriles, heterocyclic nitriles, and aliphatic nitriles were converted into the corresponding amides in good to excellent yields.
- Ma, Xiaoyun,He, Ying,Lu, Ming
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- Sodium azide as a catalyst for the hydration of nitriles to primary amides in water
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The selective conversion of aromatic nitriles to primary amides has been accomplished using sodium azide. The corresponding amides were obtained efficiently in excellent yields. This reaction was carried out under eco-friendly conditions using water in the absence of organic solvents.
- Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Roostaei, Mohsen
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- An efficient and practical protocol for catalytic hydrolysis of nitriles by a copper(I) complex in water
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The cuprous complex - Cu4I4(H2O) 4 - has been isolated and employed for the catalytic hydrolysis of arenecarbonitriles, cinnamonitrile, and arylacetonitriles to the corresponding amides in pure water in high yields of up to 98%. The catalyst can be easily recovered and reused without loss of catalytic activity at least five times. Oxindole could be prepared successfully by one-pot domino protocols based on this method. Copyright
- Li, Zhengkai,Wang, Lixia,Zhou, Xiangge
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- Silica-supported 2,4,6-trichloro-1,3,5-triazine as an efficient reagent for direct conversion of carboxylic acids to amides under solvent-free conditions
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A very simple and efficient solvent-free method for the direct conversion of carboxylic acids to primary, secondary, tertiary alkyl, and aromatic amides in the presence of the corresponding ammonium salts, silica-supported 2,4,6-trichloro-1,3,5-triazine, and triethylamine is described. The reactions proceed rapidly at room temperature, and the products are obtained in moderate to excellent yields. Copyright Taylor & Francis Group, LLC.
- Khalafi-Nezhad, Ali,Zare, Abdolkarim,Parhami, Abolfath,Rad, Mohammad Navid Soltani,Nejabat, Gholam Reza
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- Efficient method for the direct preparation of amides from carboxylic acids using tosyl chloride under solvent-free conditions
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A simple, clean and highly efficient solvent-free procedure for the preparation of primary, secondary, tertiary and aromatic amides is described from the direct reaction of carboxylic acids and silica-supported ammonium salts, triethylamine (TEA) and tosyl chloride (TsCl) as condensing agent. The reaction proceeds rapidly in high yields at room temperature.
- Khalafi-Nezhad, Ali,Parhami, Abolfath,Soltani Rad, Mohammad Navid,Zarea, Abdolkarim
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- The hydration of nitriles catalyzed by water-soluble rhodium complexes
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The water-soluble rhodium complex generated in situ from [Rh(COD)Cl]2 and P(m-C6H4SO3Na)3 has been found to be a very effective catalyst for the hydration of nitriles, under basic conditions. (C) 2000 Elsevier Science Ltd.
- Djoman, Marie Charlotte Koffi-Bié,Ajjou, Abdelaziz Nait
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- Efficient Hydration of Nitriles Promoted by Gallic Acid Derived from Renewable Bioresources
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An efficient gallic acid promoted nitriles hydration at room temperature with ethanol/water as a solvent has been developed. The present protocol offers a wide range of amides in moderate to good yields. Moreover, galla chinensis extract can serve as the promoter to perform the hydration, which also shows the potential utilization of natural feedstocks.
- Deng, Tao,Wang, Cheng-Zhang
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- 2-Diphenylphosphanyl-4-pyridyl(dimethyl)amine as an effective ligand for the ruthenium(II) complex catalyzed homogeneous hydration of nitriles under neutral conditions
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New homogeneous catalyst comprised of [Ru(methallyl)2(cod)] (cod = 1,5-cyclooctadiene) (1) and 2-diphenylphosphanyl-4-pyridyl(dimethyl)amine (2) is shown to efficiently catalyze the hydration of various nitriles under neutral conditions. The hydration proceeds in the presence of 0.5 mol% of the ruthenium catalyst at 80 °C in 1,2-dimethoxyethane solution and the corresponding amide is obtained within few hours without the formation of byproducts. Comparison of some phosphine ligands for the hydration reveals that the dimethylamino moiety of 2 improves the catalytic performance dramatically.
- Muranaka, Makoto,Hyodo, Isao,Okumura, Wataru,Oshiki, Toshiyuki
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- A heterogeneous catalytic method for the conversion of nitriles into amides using molecular sieves modified with copper(II)
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A heterogenous catalytic method is developed for the hydration of nitriles into amides with acetaldoxime. Copper(II) supported on 4 molecular sieves is an efficient catalyst for this reaction.
- Kiss, árpád,Hell, Zoltán
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- Direct preparation of primary amides from carboxylic acids and urea using imidazole under microwave irradiation
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A very simple and efficient solvent-free procedure for the preparation of primary amides is described from carboxylic acids and urea using imidazole under microwave irradiation. Various aliphatic and aromatic primary amides were prepared in good yields by this direct amidation method.
- Khalafi-Nezhad, Ali,Mokhtari, Babak,Rad, Mohammad Navid Soltani
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- A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: Aqueous hydration of nitriles to amides
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One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involves the in situ generation of magnetic silica (Fe 3O4@SiO2) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this catalyst which proceeds exclusively in aqueous medium under neutral conditions. The Royal Society of Chemistry 2012.
- Baig, R. B. Nasir,Varma, Rajender S.
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- Biotransformation of isofraxetin-6-O-β-D-glucopyranoside by Angelica sinensis (Oliv.) Diels callus
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Isofraxetin-6-O-β-D-glucopyranoside, identified from traditional medicinal herbal Xanthoceras sorbifolia Bunge, has been demonstrated to be a natural neuroinflammatory inhibitor. In order to obtain more derivatives with potential anti-neuroinflammatory effects, biotransformation was carried out. According to the characteristics of coumarin skeleton, suspension cultures of Angelica sinensis (Oliv.) Diels callus (A. sinensis callus) were employed because of the presence of diverse phenylpropanoids biosynthetic enzymes. As a result, 15 products were yielded from the suspension cultures, including a new coumarin: 8′-dehydroxymethyl cleomiscosin A (1), together with 14 known compounds. Their structures were elucidated by extensive spectroscopic analysis. Furthermore, the biotransformed pathways were discussed. Among them, compound 13 was transformed from isofraxetin-6-O-β-D-glucopyranoside, while compounds 1–6, 10–12, 14–15 were derived from the culture medium stimulated by the substrate. The biotransformation processes include hydroxylation, oxidation and esterification. Furthermore, their inhibitory effects on lipopolysaccharide (LPS)-activated nitric oxide (NO) production were evaluated in BV2 microglial cells. It is worth noting that, 1, 1′-methanediylbis(4-methoxybenzene) (3), obtucarbamates A (5), 2-nonyl-4-hydroxyquinoline N-oxide (10) and 1H-indole-3-carbaldehyde (11) exhibited significant inhibitory effect against neuroinflammation with IC50values at 1.22, 10.57, 1.02 and 0.76?μM respectively, much stronger than that of the positive control minocycline (IC5035.82?μM).
- Zhou, Di,Zhang, Yuhua,Jiang, Zhe,Hou, Yue,Jiao, Kun,Yan, Chunyan,Li, Ning
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- Cu-catalyzed aerobic oxidative C-CN bond cleavage of benzyl cyanide for the synthesis of primary amides
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An efficient method via copper-catalyzed aerobic oxidative amidation of benzyl cyanide for primary amides is successfully developed. Using readily available NH4Cl as a nitrogen source and Cu/O2 as a catalytic oxidation system offers new opportunities for C-CN bond cleavage and primary amide bond formation.
- Chen, Xiuling,Peng, Yanhong,Li, Yan,Wu, Minghu,Guo, Haibing,Wang, Jian,Sun, Shaofa
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- Electronic Substituent Effects in the Nitrilase-Catalyzed Hydrolysis of Para-Substituted Benzyl Cyanides
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The initial rates of the nitrilase (Novo)-catalyzed hydrolysis of a series of para-substituted benzyl cyanides (R = NO2, Cl, OCH3, OH, NH2) were found to be susceptible to the nature of the para-substituent of the substrate and a Hammett-type linear free energy correlation was observed with ρ = 0.96.In a separate study, effective solubilization of substituted benzyl cyanide substrates having electron-donating groups (OH, NH2, OCH3) was achieved upon mixing with β-cyclodextrin to form 1:1 mol ratio inclusion complexes, but para-substituted benzyl cyanides with electron-withdrawing groups (Cl, NO2) were not fully solubilized under the same conditions.In addition, it was shown that the presence of β-cyclodextrin not only had no inhibitory effect on the enzyme activity, but it actually increased the initial rate of hydrolysis of the unsubstituted benzyl cyanide:β-cyclodextrin inclusion complex.However, the initial rates of hydrolysis were observed to be smaller when β-cyclodextrin was added to the para-substituted benzyl cyanides.
- Geresh, Shimona,Giron, Yakir,Gilboa, Ygal,Glaser, Robert
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- Chemoselective hydration of nitriles to amides using hydrated ionic liquid (IL) tetrabutylammonium hydroxide (TBAH) as a green catalyst
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A transition metal-free process, catalyzed by tetrabutylammonium hydroxide (TBAH), has been developed for the convenient and selective hydration of nitriles to the corresponding amides. The present process converts aromatic, aliphatic, and heteroaromatic nitriles with a wide variety of functional groups into amides. The regioselective hydration of one nitrile moiety in the presence of another nitrile group gives the present protocol high impact.
- Veisi, Hojat,Maleki, Behrooz,Hamelian, Mona,Ashrafi, Samaneh Sedigh
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- HYDROLYSIS IN THE ABSENCE OF BULK WATER 1. CHEMOSELECTIVE HYDROLYSIS OF AMIDES USING TETRAHALOPHTALIC ANHYDRIDES
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The reaction of primary and secondary amides with tetrafluorophthalic or tetrachlorophtalic anhydride gives carboxylic acids in good yield.The reaction is chemoselective in that the amide functionality can be hydrolyzed in the presence of ester groups.
- Eaton, Jefferson T.,Rounds, William D.,Urbanowicz, John H.,Gribble, Gordon W.
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- Efficient and practical transition metal-free catalytic hydration of organonitriles to amides
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K2CO3 can act as an efficient catalyst for the hydration of organonitriles in aqueous conditions assisted by microwave irradiation, which represents an inexpensive, practical, atom-economical, and straightforward transition metal-free protocol to various amides.
- Tu, Tao,Wang, Zhixun,Liu, Zelong,Feng, Xike,Wang, Qingyi
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- Ruthenium on chitosan: A recyclable heterogeneous catalyst for aqueous hydration of nitriles to amides
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Ruthenium has been immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with ruthenium chloride, and has been utilized for the oxidation of nitriles to amides; the hydration of nitriles occurs in high yield and excellent selectivity, which proceeds exclusively in aqueous medium under neutral conditions. the Partner Organisations 2014.
- Baig, R. B. Nasir,Nadagouda, Mallikarjuna N.,Varma, Rajender S.
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- Solid phase synthesis of aryl amines
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A method for the solid phase synthesis of aryl amines is reported. The method involves a palladium mediated coupling reaction between aryl bromides and amines. The products are isolated in high purity and good yields. This method should prove to be a useful tool for constructing combinatorial libraries containing the aryl amine moiety.
- Willoughby, Christopher A.,Chapman, Kevin T.
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- Ti-superoxide catalyzed oxidative amidation of aldehydes with saccharin as nitrogen source: Synthesis of primary amides
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A new heterogeneous catalytic system (Ti-superoxide/saccharin/TBHP) has been developed that efficiently catalyzes oxidative amidation of aldehydes to produce various primary amides. The protocol employs saccharin as amine source and was found to tolerate a wide range of substrates with different functional groups. Moderate to excellent yields, catalyst reusability and operational simplicity are the main highlights. A possible mechanism and the role of the catalyst in oxidative amidation have also been discussed.
- Kamble, Rohit B.,Mane, Kishor D.,Rupanawar, Bapurao D.,Korekar, Pranjal,Sudalai,Suryavanshi, Gurunath
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- Facile desulfurization of thioamides and thioureas with tetrabutylammonium periodate under mild conditions
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Thioamides and thioureas were reacted with tetrabutylammonium periodate at room temperature to afford the corresponding amides and ureas, respectively, under aprotic conditions. Springer-Verlag 2005.
- Pourali, Ali Reza
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- Transition metal-free 1,3-dimethylimidazolium hydrogen carbonate catalyzed hydration of organonitriles to amides
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An efficient hydration of organonitriles to the corresponding amides was accomplished using 1,3-dimethylimidazolium hydrogen carbonate as an organocatalyst. The developed catalytic method was also applicable for the synthesis of metal phthalocyanines.
- Verma, Praveen Kumar,Sharma, Upendra,Bala, Manju,Kumar, Neeraj,Singh, Bikram
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- A facile hydration of nitriles by dimethyldioxirane
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A new and practical method for the conversion of nitriles to amides by employing the dimethyldioxirane, which is prepared in situ from acetone and oxone, is described.
- Bose, D. Subhas,Baquer, Syed M.
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- Selective hydrolysis of nitriles to amides using NaOH-PEG under microwave irradiation
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We describe here an efficient, rapid and selective method for the conversion of nitriles in to their corresponding amides in the presence of PEG-400, aqueous sodium hydroxide system under microwave irradiation.
- Bendale, Pravin M.,Khadilkar, Bhushan M.
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- A continuous-flow synthesis of primary amides from hydrolysis of nitriles using hydrogen peroxide as oxidant
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A continuous-flow synthesis of primary amides from hydrolysis of nitriles using hydrogen peroxide as oxidant has been developed. Using this procedure, a variety of nitriles could be smoothly transformed into the desired primary amides in good to excellent yields. The mild reaction conditions and the flowing reaction system greatly improved the safety and make the reaction easy to scale up.
- Zhan, Wei,Ji, Ling,Ge, Ze-mei,Wang, Xin,Li, Run-tao
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- Direct catalytic formation of primary and tertiary amides from non-activated carboxylic acids, employing carbamates as amine source
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The operationally simple titanium(IV)- or zirconium(IV)-catalyzed direct amidation of non-activated carboxylic acids with ammonium carbamates generates primary, and tertiary N,N-dimethyl-substituted amides in good to excellent yields. Copyright
- Tinnis, Fredrik,Lundberg, Helena,Adolfsson, Hans
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- Selective Cleavage of Inert Aryl C-N Bonds in N-Aryl Amides
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A highly selective, IBX-promoted reaction has been developed for the oxidative cleavage of inert C(aryl)-N bonds on secondary amides while leaving the C(carbonyl)-N bond unchanged. This metal-free reaction proceeds under mild conditions (HFIP/H2O, 25 °C), providing facile access to various useful primary amides, some of which would be otherwise unattainable using conventional aminolysis and hydrolysis approaches.
- Zhang, Zhiguo,Zheng, Dan,Wan, Yameng,Zhang, Guisheng,Bi, Jingjing,Liu, Qingfeng,Liu, Tongxin,Shi, Lei
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- Synthesis of and catalytic nitrile hydration by a cationic tris(μ-hydroxo)diruthenium(II) complex having PMe3ligands
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While phenyl vinyl ether does not react with [Ru(η4-1,5-COD)(η6-1,3,5-COT)] (1)/PMe3, the C–O bond cleavage of phenyl vinyl ether occurs by 1/PMe3in the presence of water to give a tris(μ-hydroxo)diruthenium(II) complex [(Me3P)3Ru(μ-OH)3Ru(PMe3)3]+[OPh]?·HOPh (3·HOPh) with evolution of ethylene. The molecular structure of 3·HOPh is unequivocally determined by X-ray analysis. The most likely mechanism for the formation of 3·HOPh is protonation of [Ru(η4-1,5-COD)(PMe3)3] (2c) by water and subsequent insertion of phenyl vinyl ether into the resulting Ru–H bond followed by the β-phenoxide elimination and hydrolysis and dimerization of the phenoxoruthenium(II) species. Complex 3 acts as a catalyst for nitrile hydration. As a typical example, the hydration of benzonitrile was achieved by 3 (1.0 mol%) in 1,4-dioxane at 120 °C for 6 h to give benzamide quantitatively.
- Kiyota, Sayori,Kobori, Takako,Soeta, Hirofumi,Ichikawa, You-ichi,Komine, Nobuyuki,Komiya, Sanshiro,Hirano, Masafumi
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- Direct and facile synthesis of primary amides from carboxylic acids via acyl isocyanate intermediates using mukaiyama reagent
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A very simple and efficient procedure for the preparation of primary amides is described from carboxylic acids using Mukaiyama reagent/KNCO in aqueous acetonitrile. Availability of the reagents, simplicity, and easy workup of the reaction crude make this method attractive for organic chemists.
- Azadi, Roya,Motamedpoor, Zahra
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- Hydration of nitriles to amides by a chitin-supported ruthenium catalyst
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Chitin-supported ruthenium (Ru/chitin) promotes the hydration of nitriles to carboxamides under aqueous conditions. The nitrile hydration can be performed on a gram-scale and is compatible with the presence of various functional groups including olefins, aldehydes, carboxylic esters and nitro and benzyloxycarbonyl groups. The Ru/chitin catalyst is easily prepared from commercially available chitin, ruthenium(III) chloride and sodium borohydride. Analysis of Ru/chitin by high-resolution transmission electron microscopy indicates the presence of ruthenium nanoparticles on the chitin support.
- Matsuoka, Aki,Isogawa, Takahiro,Morioka, Yuna,Knappett, Benjamin R.,Wheatley, Andrew E. H.,Saito, Susumu,Naka, Hiroshi
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- Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)2/Lewis Acid Catalyst at Ambient Temperature
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Transition-metal-catalyzed nitrile hydration is an atom-economic method for the synthesis of various amides. This work demonstrates for the first time that the addition of non-redox metal ions like Sc3+ dramatically accelerate the hydration of various nitriles to amides at ambient temperature with the simple Pd(OAc)2 salt as catalyst, whereas the reactions with Pd(OAc)2 alone were very sluggish. The formation of a heterobimetallic PdII/ScIII species has been proposed as the key species for the hydration that demonstrates a bimetallic synergistic effect in this process.
- Zhang, Sicheng,Xu, Haosheng,Lou, Chenlin,Senan, Ahmed M.,Chen, Zhuqi,Yin, Guochuan
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- Nitrogen Atom Transfer Catalysis by Metallonitrene C?H Insertion: Photocatalytic Amidation of Aldehydes
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C?H amination and amidation by catalytic nitrene transfer are well-established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C?H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd?N) with a diradical nitrogen ligand that is singly bonded to PdII. Despite the subvalent nitrene character, selective C?H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N3SiMe3. Based on these results, a photocatalytic protocol for aldehyde C?H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C?H nitrogen atom transfer offers facile access to primary amides after deprotection.
- Schmidt-R?ntsch, Till,Verplancke, Hendrik,Lienert, Jonas N.,Demeshko, Serhiy,Otte, Matthias,Van Trieste, Gerard P.,Reid, Kaleb A.,Reibenspies, Joseph H.,Powers, David C.,Holthausen, Max C.,Schneider, Sven
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- Method for preparing primary and secondary amide compounds
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The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for preparing primary and secondary amide compounds. The method for preparing primary and secondary amide compounds comprises the following steps of carrying out catalytic reduction on an N-substituted amide compound at 30-130 DEG C by using a protic solvent as a reduction reagent and a dichloro(p-methyl isopropylbenzene) ruthenium (II) dimer complex as a catalyst to obtain a reaction solution after the reduction reaction is finished, and carrying out post-treatment on the reaction solution to obtain the corresponding primary amide compound or secondary amide compound. According to the method for preparing the primary and secondary amide compounds, the transfer hydrogenation reaction of nitrogen-oxygen and nitrogen-carbon bonds is realized, the reaction conditions are mild and simple, the substrate application range is wide, the operation is convenient, and the corresponding primary amide compound or secondary amide compound is obtained with high efficiency and high selectivity.
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Paragraph 0090-0100
(2021/02/06)
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- Manganese-Pincer-Catalyzed Nitrile Hydration, α-Deuteration, and α-Deuterated Amide Formation via Metal Ligand Cooperation
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A simple and efficient system for the hydration and α-deuteration of nitriles to form amides, α-deuterated nitriles, and α-deuterated amides catalyzed by a single pincer complex of the earth-abundant manganese capable of metal-ligand cooperation is reported. The reaction is selective and tolerates a wide range of functional groups, giving the corresponding amides in moderate to good yields. Changing the solvent from tert-butanol to toluene and using D2O results in formation of α-deuterated nitriles in high selectivity. Moreover, α-deuterated amides can be obtained in one step directly from nitriles and D2O in THF. Preliminary mechanistic studies suggest the transformations contributing toward activation of the nitriles via a metal-ligand cooperative pathway, generating the manganese ketimido and enamido pincer complexes as the key intermediates for further transformations.
- Ben-David, Yehoshoa,Diskin-Posner, Yael,Kar, Sayan,Milstein, David,Zhou, Quan-Quan,Zou, You-Quan
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p. 10239 - 10245
(2021/08/24)
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- Hydration of Aliphatic Nitriles Catalyzed by an Osmium Polyhydride: Evidence for an Alternative Mechanism
-
The hexahydride OsH6(PiPr3)2 competently catalyzes the hydration of aliphatic nitriles to amides. The main metal species under the catalytic conditions are the trihydride osmium(IV) amidate derivatives OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2, which have been isolated and fully characterized for R = iPr and tBu. The rate of hydration is proportional to the concentrations of the catalyst precursor, nitrile, and water. When these experimental findings and density functional theory calculations are combined, the mechanism of catalysis has been established. Complexes OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2 dissociate the carbonyl group of the chelate to afford κ1-N-amidate derivatives, which coordinate the nitrile. The subsequent attack of an external water molecule to both the C(sp) atom of the nitrile and the N atom of the amidate affords the amide and regenerates the κ1-N-amidate catalysts. The attack is concerted and takes place through a cyclic six-membered transition state, which involves Cnitrile···O-H···Namidate interactions. Before the attack, the free carbonyl group of the κ1-N-amidate ligand fixes the water molecule in the vicinity of the C(sp) atom of the nitrile.
- Babón, Juan C.,Esteruelas, Miguel A.,López, Ana M.,O?ate, Enrique
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p. 7284 - 7296
(2021/05/29)
-
- A CO2-mediated base catalysis approach for the hydration of triple bonds in ionic liquids
-
Herein, we report a CO2-mediated base catalysis approach for the activation of triple bonds in ionic liquids (ILs) with anions that can chemically capture CO2 (e.g., azolate, phenolate, and acetate), which can achieve hydration of triple bonds to carbonyl chemicals. It is discovered that the anion-complexed CO2 could abstract one proton from proton resources (e.g., IL cation) and transfer it to the CN or CC bonds via a six-membered ring transition state, thus realizing their hydration. In particular, tetrabutylphosphonium 2-hydroxypyridine shows high efficiency for hydration of nitriles and CC bond-containing compounds under a CO2 atmosphere, affording a series of carbonyl compounds in excellent yields. This catalytic protocol is simple, green, and highly efficient and opens a new way to access carbonyl compounds via triple bond hydration under mild and metal-free conditions.
- Han, Buxing,Ke, Zhengang,Li, Ruipeng,Liu, Zhimin,Tang, Minhao,Wang, Yuepeng,Zeng, Wei,Zhang, Fengtao,Zhao, Yanfei
-
supporting information
p. 9870 - 9875
(2021/12/27)
-
- A Molecular Iron-Based System for Divergent Bond Activation: Controlling the Reactivity of Aldehydes
-
The direct synthesis of amides and nitriles from readily available aldehyde precursors provides access to functional groups of major synthetic utility. To date, most reliable catalytic methods have typically been optimized to supply one product exclusively. Herein, we describe an approach centered on an operationally simple iron-based system that, depending on the reaction conditions, selectively addresses either the C=O or C-H bond of aldehydes. This way, two divergent reaction pathways can be opened to furnish both products in high yields and selectivities under mild reaction conditions. The catalyst system takes advantage of iron's dual reactivity capable of acting as (1) a Lewis acid and (2) a nitrene transfer platform to govern the aldehyde building block. The present transformation offers a rare control over the selectivity on the basis of the iron system's ionic nature. This approach expands the repertoire of protocols for amide and nitrile synthesis and shows that fine adjustments of the catalyst system's molecular environment can supply control over bond activation processes, thus providing easy access to various products from primary building blocks.
- Chatterjee, Basujit,Jena, Soumyashree,Chugh, Vishal,Weyhermüller, Thomas,Werlé, Christophe
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p. 7176 - 7185
(2021/06/30)
-
- Mechanochemical Synthesis of Primary Amides
-
Ball milling of aromatic, heteroaromatic, vinylic, and aliphatic esters with ethanol and calcium nitride afforded the corresponding primary amides in a transformation that was compatible with a variety of functional groups and maintained the integrity of a stereocenter α to carbonyl. This methodology was applied to α-amino esters and N-BOC dipeptide esters and also to the synthesis of rufinamide, an antiepileptic drug.
- Gómez-Carpintero, Jorge,Sánchez, J. Domingo,González, J. Francisco,Menéndez, J. Carlos
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p. 14232 - 14237
(2021/10/20)
-
- Aerobic oxidation of primary amines to amides catalyzed by an annulated mesoionic carbene (MIC) stabilized Ru complex
-
Catalytic aerobic oxidation of primary amines to the amides, using the precatalyst [Ru(COD)(L1)Br2] (1) bearing an annulated π-conjugated imidazo[1,2-a][1,8]naphthyridine-based mesoionic carbene ligand L1, is disclosed. This catalytic protocol is distinguished by its high activity and selectivity, wide substrate scope and modest reaction conditions. A variety of primary amines, RCH2NH2 (R = aliphatic, aromatic and heteroaromatic), are converted to the corresponding amides using ambient air as an oxidant in the presence of a sub-stoichiometric amount of KOtBu in tBuOH. A set of control experiments, Hammett relationships, kinetic studies and DFT calculations are undertaken to divulge mechanistic details of the amine oxidation using 1. The catalytic reaction involves abstraction of two amine protons and two benzylic hydrogen atoms of the metal-bound primary amine by the oxo and hydroxo ligands, respectively. A β-hydride transfer step for the benzylic C-H bond cleavage is not supported by Hammett studies. The nitrile generated by the catalytic oxidation undergoes hydration to afford the amide as the final product. This journal is
- Yadav, Suman,Reshi, Noor U Din,Pal, Saikat,Bera, Jitendra K.
-
p. 7018 - 7028
(2021/11/17)
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- Metal-Free Synthesis of Alkenylazaarenes and 2-Aminoquinolines through Base-Mediated Aerobic Oxidative Dehydrogenation of Benzyl Alcohols
-
A metal-free, base-mediated, and atom-efficient oxidative dehydrogenative coupling of substituted phenylmethanols (benzyl alcohols) with methyl azaarenes or phenylacetonitriles to afford substituted alkenylazaarenes or 2-aminoquinolines, respectively is described. CsOH.H2O was discovered to be the base of choice for obtaining optimal yields of the title compounds, although the reaction could proceed with KOH as well. The protocol that works efficiently in the presence of air is amenable over broad range of substrates.
- Batra, Sanjay,Dahatonde, Dipak J.,Ghosh, Aritra
-
supporting information
p. 2746 - 2751
(2021/06/25)
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- One-pot method for the synthesis of 1-aryl-2-aminoalkanol derivatives from the corresponding amides or nitriles
-
We have identified a novel one-pot method for the synthesis of β-amino alcohols, which is based on C-H bond hydroxylation at the benzylic α-carbon atom with a subsequent nitrile or amide functional group reduction. This cascade process uses molecular oxygen as an oxidant and sodium bis(2-methoxyethoxy)aluminum hydride as a reductant. The substrate scope was examined on 30 entries and, although the respective products were provided in moderate yields only, the above simple protocol may serve as a direct and powerful entry to the sterically congested 1,2-amino alcohols that are difficult to prepare by other routes. The plausible mechanistic rationale for the observed results is given and the reaction was applied to a synthesis of a potentially bioactive target. This journal is
- Bobal, Pavel,Otevrel, Jan,Svestka, David
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p. 25029 - 25045
(2020/07/14)
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- Fe3O4@GlcA@Cu-MOF: A Magnetic Metal-Organic Framework as a Recoverable Catalyst for the Hydration of Nitriles and Reduction of Isothiocyanates, Isocyanates, and Isocyanides
-
A novel magnetic metal-organic framework (Fe3O4@GlcA@Cu-MOF) has been prepared and characterized by spectroscopic, microscopic, and magnetic techniques. This magnetically separable catalyst exhibited high catalytic activity for nitrile hydration and the ability to reduce isothiocyanates, isocyanates, and isocyanides with excellent activity and selectivity without any additional reducing agent.
- Ghorbani-Choghamarani, Arash,Taherinia, Zahra
-
supporting information
p. 902 - 909
(2020/11/30)
-
- Multi-target inhibitor acting on QC and GSK-3[beta]
-
The invention discloses a multi-target inhibitor acting on QC and GSK-3[beta], wherein the multi-target inhibitor has the structural general formula shown in the specification; according to active center crystal structures of target QC and GSK-3[beta] zymoprotein, with synthesis of multiple high-activity pharmacophores, the multi-target inhibitor capable of acting on QC and GSK-3[beta] at the sametime is prepared through skeletal transition and recombination design; the multi-target inhibitor is a high-activity molecule with multiple target points, the molecular structure diversity of a leaddrug is remarkably expanded, and research and development of innovative anti-AD drugs and AD diagnostic kits are actively promoted.
- -
-
Paragraph 0049; 0052
(2020/04/02)
-
- Preparation method and application of multi-target inhibitor acting on QC and GSK-3beta
-
The invention discloses a preparation method and application of a multi-target inhibitor acting on QC and GSK-3 beta. The structural general formula of the multi-target inhibitor prepared by the method is shown in the specification. According to the invention, according to active center crystal structures of target QC and GSK-3 beta zymoprotein, multiple high-activity pharmacophores are integrated, the multi-target inhibitor capable of acting on QC and GSK-3 beta at the same time is prepared through framework transition and recombination design, the multi-target inhibitor is molecules with multiple target points and high activity, the molecular structure diversity of a lead drug is remarkably expanded, and the research and development of innovative anti-AD drugs and AD diagnostic kits areactively promoted, and the preparation method of the multi-target inhibitor provided by the invention is simple and easy to operate.
- -
-
Paragraph 0058; 0061
(2020/04/17)
-
- Direct synthesis of amides from nonactivated carboxylic acids using urea as nitrogen source and Mg(NO3)2or imidazole as catalysts
-
A new method for the direct synthesis of primary and secondary amides from carboxylic acids is described using Mg(NO3)2·6H2O or imidazole as a low-cost and readily available catalyst, and urea as a stable, and easy to manipulate nitrogen source. This methodology is particularly useful for the direct synthesis of primary and methyl amides avoiding the use of ammonia and methylamine gas which can be tedious to manipulate. Furthermore, the transformation does not require the employment of coupling or activating agents which are commonly required.
- Blacker, A. John,Chhatwal, A. Rosie,Lomax, Helen V.,Marcé, Patricia,Williams, Jonathan M. J.
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p. 5808 - 5818
(2020/06/21)
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- Amine-boranes as Dual-Purpose Reagents for Direct Amidation of Carboxylic Acids
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Amine-boranes serve as dual-purpose reagents for direct amidation, activating aliphatic and aromatic carboxylic acids and, subsequently, delivering amines to provide the corresponding amides in up to 99% yields. Delivery of gaseous or low-boiling amines as their borane complexes provides a major advantage over existing methodologies. Utilizing amine-boranes containing borane incompatible functionalities allows for the preparation of functionalized amides. An intermolecular mechanism proceeding through a triacyloxyborane-amine complex is proposed.
- Choudhary, Shivani,Hamann, Henry J.,Ramachandran, P. Veeraraghavan
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supporting information
(2020/11/13)
-
- Transamidation for the Synthesis of Primary Amides at Room Temperature
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Various primary amides have been synthesized using the transamidation of various tertiary amides under metal-free and mild reaction conditions. When (NH4)2CO3 reacts with a tertiary amide bearing an N-electron-withdrawing substituent, such as sulfonyl and diacyl, in DMSO at 25 °C, the desired primary amide product is formed in good yield with good funcctional group tolerance. In addition, N-tosylated lactam derivatives afforded their corresponding N-tosylamido alkyl amide products via a ring opening reaction.
- Chen, Jiajia,Lee, Sunwoo,Xia, Yuanzhi
-
supporting information
(2020/05/05)
-
- Synthesis of β-hydroxyamides through ruthenium-catalyzed hydration/transfer hydrogenation of β-ketonitriles in water: Scope and limitations
-
A cascade process for the straightforward one-pot conversion of β-ketonitriles into β-hydroxyamides is presented. The process, that proceeds in water employing the arene-ruthenium(II) complex [RuCl2(η6-p-cymene){P(4-C6H4F)2Cl}] as catalyst in combination with sodium formate, involves the initial hydration of the β-ketonitrile substrates to generate the corresponding β-ketoamide intermediates, which subsequently undergo the transfer hydrogenation (TH) of the carbonyl group. Employing a family of forty different β-ketonitriles, featuring diverse substitution patterns, the scope and limitations of the process have been established.
- González-Fernández, Rebeca,Crochet, Pascale,Cadierno, Victorio
-
-
- Hydration of nitriles using a metal-ligand cooperative ruthenium pincer catalyst
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Nitrile hydration provides access to amides that are important structural elements in organic chemistry. Here we report catalytic nitrile hydration using ruthenium catalysts based on a pincer scaffold with a dearomatized pyridine backbone. These complexes catalyze the nucleophilic addition of H2O to a wide variety of aliphatic and (hetero)aromatic nitriles in tBuOH as solvent. Reactions occur under mild conditions (room temperature) in the absence of additives. A mechanism for nitrile hydration is proposed that is initiated by metal-ligand cooperative binding of the nitrile.
- Guo, Beibei,Otten, Edwin,De Vries, Johannes G.
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p. 10647 - 10652
(2019/12/02)
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- Metal-free nitrogen -doped carbon nanosheets: A catalyst for the direct synthesis of imines under mild conditions
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Herein, a highly stable, porous, multifunctional and metal-free catalyst was developed, which exhibited significant catalytic performance in the oxidation of amines and transfer hydrogenation of nitriles under mild conditions; this could be attributed to the presence of numerous active sites and their outstanding BET surface area. The obtained results showed that most of the yields of imines exceeded 90%, and the cycling performance of the catalyst could be at least seven runs without any decay in the reaction activity, which could be comparable to those of metal catalysts. Subsequently, a kinetic study has demonstrated that the apparent activation energy for the direct synthesis of imines from amines is 67.39 kJ mol-1, which has been performed to testify that the catalytic performances are rational. Via catalyst characterizations and experimental data, graphitic-N has been proven to be the active site of the catalyst. Hence, this study is beneficial to comprehend the mechanism of action of a metal-free N-doped carbon catalyst in the formation of imines.
- Wang, Kaizhi,Jiang, Pengbo,Yang, Ming,Ma, Ping,Qin, Jiaheng,Huang, Xiaokang,Ma, Lei,Li, Rong
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p. 2448 - 2461
(2019/05/17)
-
- Dehydrogenative Synthesis of Quinolines, 2-Aminoquinolines, and Quinazolines Using Singlet Diradical Ni(II)-Catalysts
-
Simple, straightforward, and atom economic methods for the synthesis of quinolines, 2-aminoquinolines, and quinazolines via biomimetic dehydrogenative condensation/coupling reactions, catalyzed by well-defined inexpensive and easy to prepare singlet diradical Ni(II)-catalysts featuring two antiferromagnetically coupled singlet diradical diamine type ligands are described. Various polysubstituted quinolines, 2-aminoquinolines, and quinazolines were synthesized in moderate to good yields from different low-cost and readily accessible starting materials. Several control experiments were carried out to get insight into the reaction mechanism which shows that the nickel and the coordinated diamine ligands participate in a synergistic way during the dehydrogenation of alcohols.
- Chakraborty, Gargi,Sikari, Rina,Das, Siuli,Mondal, Rakesh,Sinha, Suman,Banerjee, Seemika,Paul, Nanda D.
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p. 2626 - 2641
(2019/02/26)
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- One-Pot Anodic Conversion of Symmetrical Bisamides of Ethylene Diamine to Unsymmetrical gem-Bisamides of Methylene Diamine
-
Symmetrical bisamides of ethylene diamine of type ArCONHCH2CH2NHCOAr undergo anodic C-C bond cleavage in acetonitrile-LiClO4 under controlled-potential electrolysis. The electrogenerated carbocation intermediates react with the solvent acetonitrile to afford unsymmetrical gem-bisamides of type ArCONHCH2NHCOMe in a one-pot reaction. The yields of the latter products are moderate (up to 60%). Other minor products involve two symmetrical gem-bisamides of type ArCONHCH2NHCOAr and MeCONHCH2NHCOMe and fragmentation products (e.g., ArCONHCHO, ArCONH2, and ArCN).
- Golub, Tatiana,Dou, Gui-Yuan,Zeng, Cheng-Chu,Becker, James Y.
-
supporting information
p. 7961 - 7964
(2019/10/11)
-
- Potassium tert-Butoxide Prompted Highly Efficient Transamidation and Its Coordination Radical Mechanism
-
A simple and highly efficient protocol was developed for the transamidation of N,N-disubstituted amides with primary amines in the presence of tBuOK, affording desired products in good to excellent yields. This reaction proceeded under nitrogen atmosphere and featured extensive substrate tolerance. Experimental investigation suggested that a coordination radical process enhanced this transformation.
- Tan, Zhiyong,Li, Zhenhua,Ma, Yao,Qin, Jinjing,Yu, Chuanming
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p. 4538 - 4545
(2019/07/18)
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- Magnetic Nanoparticle-Supported Cu–NHC Complex as an Efficient and Recoverable Catalyst for Nitrile Hydration
-
Magnetic nanoparticles supported N-heterocyclic carbene–Cu complex was prepared and authenticated by FT-IR, SEM, EDX, VSM, powder-XRD. The catalytic activity of these magnetically retrievable NPs was investigated for hydration of nitriles as the simplest route for the synthesis of amides in an atom-economical manner. A wide range of nitriles containing various functional groups such as olefin, aldehyde, nitro, carboxylic acid was examined in this transformation to generate their corresponding amides in the aqueous medium. The immobilized catalyst was easily recovered using an external magnet and reused for six times without significant loss of its catalytic activity. Graphical Abstract: [Figure not available: see fulltext.].
- Kazemi Miraki, Maryam,Arefi, Marzban,Salamatmanesh, Arefeh,Yazdani, Elahe,Heydari, Akbar
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p. 3378 - 3388
(2018/09/11)
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- [18F]MALEIMIDE-BASED GLYCOGEN SYNTHASE KINASE-3BETA LIGANDS FOR POSITRON EMISSION TOMOGRAPHY IMAGING AND RADIOSYNTHESIS METHOD
-
The present invention provides a compound having the structure: (Formula I), and a method of inhibiting Glycogen synthase kinase-3 β (GSK-3β) in a subject comprising administering to the subject said compound, so as to thereby inhibit the GSK-3β in the subject.
- -
-
Page/Page column 69; 70
(2018/08/03)
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- 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.
- -
-
Paragraph 0138; 0139; 0140; 0141; 0142
(2018/05/07)
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- Trinuclear complexes of palladium(II) with chalcogenated N-heterocyclic carbenes: Catalysis of selective nitrile-primary amide interconversion and Sonogashira coupling
-
3-Methyl-1-(2-(phenylthio/seleno)ethyl)-1H-benzo[d]imidazol-3-ium iodide (L1/L2), a precursor of sulfated/selenated N-heterocyclic carbene, was synthesized by the reaction of benzimidazole with 1,2-dichloroethane followed by treatment with PhS/SeNa and MeI. The reaction of L1/L2 with Ag2O followed by treatment with [Pd(CH3CN)2Cl2] (metal to ligand ratio 3:2), i.e. transmetallation, resulted in trinuclear palladium(ii) complexes [Pd3(L1/L2-HI)2(CH3CN)Cl6] (1-2). The complexes were characterized with 1H, 13C{1H} and 77Se{1H} NMR (2 only), elemental analyses, HR-MS and single-crystal X-ray diffraction. The geometry of three Pd atoms in each complex is nearly square planar. The Pd-S/Se, Pd-C, Pd-N and Pd-Cl bond distances (?) in 1/2 are 2.3179(19)/2.4312(10), 1.968(7)/1.952(4), 2.073(8)/2.079(4) and 2.2784(19)-2.298(2)/2.292(2)-2.3003(15), respectively. In both the complexes, all Cl are trans to each other. For the central Pd atom, two benzimidazole rings are also trans to each other. The C-H?Cl non-covalent interactions result in a three-dimensional network. The moisture and air insensitive trinuclear Pd(ii) complexes 1 and 2 are thermally stable and efficient as a catalyst for nitrile-amide interconversion and amine-free Sonogashira C-C coupling (in the presence of CuI). The optimum temperature is 80 °C for the interconversion and 110 °C for the coupling. The catalytic protocols are applicable to both aliphatic and aromatic amides/nitriles. The optimum catalyst loading is 1 mol% for the C-C coupling and 0.5 to 1 mol% for the interconversion. K2CO3 as a base gives the best result for Sonogashira C-C coupling. In the conversion of nitriles to amides, the formation of an acid was not detected. After using once, 1/2 can carry out the conversion of ten fresh lots of nitriles to amides with almost the same efficiency. The real catalytic species for the interconversion and coupling appear to be based on Pd(ii) and Pd(0), respectively.
- Dubey, Pooja,Gupta, Sonu,Singh, Ajai K.
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p. 13065 - 13076
(2017/10/13)
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- A Brevibacterium process for synthesizing amide
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The invention discloses a method for synthesizing amide through nitrile hydrolysis. The method comprises the following steps: adding nitrile, acetaldoxime, water, a water-soluble rhodium complex to a reaction vessel, and cooling to room temperature after reaction of a reaction mixture for several hours at the temperature of 50-80 DEG C; and adding ethyl acetate for extraction so as to obtain an organic layer, and carrying out rotary evaporation to remove a solvent, thus obtaining a target product. Compared with a method for synthesizing amide through nitrile hydrolysis by using oxime as a water source in a transition metal catalysis process, the method has the advantages that a used catalyst is low in loading and does not contain a phosphine ligand seriously polluting environments, synthesis can be performed in air, and nitrogen protection is not needed; and therefore, the method meets the green chemistry requirements and has a wide development prospect.
- -
-
Paragraph 0085; 0086; 0087; 0088
(2017/04/29)
-
- Development of [18F]Maleimide-Based Glycogen Synthase Kinase-3β Ligands for Positron Emission Tomography Imaging
-
Dysregulation of glycogen synthase kinase-3β (GSK-3β) is implicated in the pathogenesis of neurodegenerative and psychiatric disorders. Thus, development of GSK-3β radiotracers for positron emission tomography (PET) imaging is of paramount importance, because such a noninvasive imaging technique would allow better understanding of the link between the activity of GSK-3β and central nervous system disorders in living organisms, and it would enable early detection of the enzyme’s aberrant activity. Herein, we report the synthesis and biological evaluation of a series of fluorine-substituted maleimide derivatives that are high-affinity GSK-3β inhibitors. Radiosynthesis of a potential GSK-3β tracer [18F]10a is achieved. Preliminary in vivo PET imaging studies in rodents show moderate brain uptake, although no saturable binding was observed in the brain. Further refinement of the lead scaffold to develop potent [18F]-labeled GSK-3 radiotracers for PET imaging of the central nervous system is warranted.
- Hu, Kongzhen,Patnaik, Debasis,Collier, Thomas Lee,Lee, Katarzyna N.,Gao, Han,Swoyer, Matthew R.,Rotstein, Benjamin H.,Krishnan, Hema S.,Liang, Steven H.,Wang, Jin,Yan, Zhiqiang,Hooker, Jacob M.,Vasdev, Neil,Haggarty, Stephen J.,Ngai, Ming-Yu
-
p. 287 - 292
(2017/03/17)
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- Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex
-
A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.
- You, Tingjie,Wang, Zhenrong,Chen, Jiajia,Xia, Yuanzhi
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p. 1340 - 1346
(2017/02/10)
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- Method for preparing amide by metallic sodium catalyzed ester ammonolysis reaction
-
The invention discloses a method for preparing amide by metallic sodium catalyzed ester ammonolysis reaction. The method is characterized in that ester and liquid ammonia are taken as raw materials, and metallic sodium is taken as a catalyst to perform reaction at a temperature of 90-140 DEG C in a high-pressure kettle; a molar ratio of the ester to ammonium is 1: (1.2 to 5.0); molar weight of the metallic sodium is 4-10% that of the ester; when reaction pressure is not lowered any longer, reaction is stopped to recycle the ammonium which is not reacted; and an obtained reaction product is post-treated to obtain a product. The method can be used for efficiently preparing the amide; and moreover, the raw materials are cheap and are low in toxicity, reaction activity is relatively high, dose of the catalyst is small, reaction speed is high, a reaction conversion rate is high, and the product is easily separated.
- -
-
Paragraph 0066
(2017/08/30)
-
- Synthesis of aryl anilinomaleimide based derivatives as glycogen synthase kinase-3β inhibitors with potential role as antidepressant agents
-
A series of aryl anilinomaleimide based derivatives has been synthesized and evaluated for in vitro glycogen synthase kinase-3β (GSK-3β) inhibitory activity. A large number of compounds from the series exhibited moderate to potent inhibitory activity against GSK-3β, with more than one-third of the compounds showing inhibition with IC50 values 50 values of 0.09, 0.12, 0.17, 0.19, 0.21 and 0.23 μM respectively), were further investigated for antidepressant activity by the widely accepted forced swim test and tail suspension test (FST and TST) models. All the tested compounds displayed antidepressant-like effects, particularly compounds 8j and 8b, which exhibited significant antidepressant activity, about 1.4-fold higher than fluoxetine, a standard antidepressant drug in both FST and TST. Preliminary structure-activity relationships have also been generated based on the experimental data obtained.
- Tantray, Mushtaq A.,Khan, Imran,Hamid, Hinna,Alam, Mohammad Sarwar,Dhulap, Abhijeet,Kalam, Abul
-
p. 6109 - 6119
(2016/07/16)
-
- A method of preparing amide compounds
-
The invention belongs to the field of organic compound preparation, and particularly relates to a method for preparing an amide compound. Specifically, cyano compounds are subjected to selective hydrolysis with a mixed solvent of a protic solvent and a non protonic solvent as a reaction medium under the conditions of heating and alkaline catalysis in the air atmosphere, so as to efficiently produce corresponding amide compounds; at the same time, carbon-carbon coupling reaction can be further utilized to react a compound containing cyano group and halogen group with a boronic acid compound, so as to prepare coupled amide compound through a one-step preparation method. The method avoids the usage of traditional toxic and harmful oxidants such as hydrogen peroxide, and is simple, efficient and green synthesis method for preparing the amide compound.
- -
-
Paragraph 0037-0038
(2017/02/09)
-
- Supported Gold Nanoparticles-Catalyzed Microwave-Assisted Hydration of Nitriles to Amides under Base-Free Conditions
-
Polystyrene-supported gold (Au@PS) nanoparticles were synthesized by the reduction deposition approach and well characterized by UV-visible, XRD, TEM, SAED, EDX, and XPS studies. The Au@PS was applied as catalyst for the hydration of nitriles to amides in water under microwave irradiation. Several functionalized aromatic, heterocyclic and aliphatic nitriles were found to be active for synthesis of the corresponding amides where no activation of water by base, ligand and support is needed. Easy recovery, negligible leaching and recyclability for up to eight runs are added advantages of the catalyst under water-mediated reaction conditions. (Figure presented.).
- Kumar, Sandeep,Sharma, Saurabh,Das, Pralay
-
supporting information
p. 2889 - 2894
(2016/09/16)
-
- Clean synthesis of primary to tertiary carboxamides by CsOH-catalyzed aminolysis of nitriles in water
-
Using CsOH as the only catalyst and utilizing its "cesium effect", a clean synthesis of a wide range of primary, secondary, and tertiary carboxamides was achieved by aminolysis reactions of nitriles with ammonia, primary, or secondary amines in water. Studies on the control reactions revealed that the reactions with ammonia most probably proceed via an aminolysis path by the initial addition of ammonia to Cs-activated nitriles to form unsubstituted amidine intermediates, while the reactions with primary or secondary amines may proceed via a hydration/transamidation path by the initial hydration of the Cs-activated nitriles to form primary carboxamide intermediates followed by their transamidation with amines through the formation of substituted amidine intermediates.
- Li, Yang,Chen, Haonan,Liu, Jianping,Wan, Xujun,Xu, Qing
-
supporting information
p. 4865 - 4870
(2016/10/06)
-
- A method from the aldehyde amide
-
The invention discloses a method for synthesizing amides from aldehyde. The method comprises the following steps: adding aldehyde, hydroxylamine hydrochloride, alkali and water to a reaction vessel to react at room temperature for half an hour; adding a water-soluble iridium complex after aldehyde is completely transformed into oxime, cooling a reactant to the room temperature after the reaction mixture reacts at 80-120 DEG C for several hours, removing water through selective evaporation, and obtaining a target product through column separation. Compared with existing methods for synthesizing amides by generating oxime through one-pot reaction between aldehyde and hydroxylamine in water and then carrying out rearrangement, the method has the advantages that the used catalyst is low in load and does not contain phosphine ligands severely polluting the environment, so that the reaction can be carried out in the air, without nitrogen protection; therefore the reaction meets the green chemical requirements and has an extensive development prospect.
- -
-
Paragraph 0051; 0052; 0053; 0054
(2017/04/08)
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- Ferric perchlorate-mediated one-step reaction of [60]fullerene with primary amides for the synthesis of fullerooxazoles
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The facile one-step reaction of [60]fullerene with primary amides promoted by cheap and easily available ferric perchlorate afforded a series of interesting fullerooxazole derivatives. The reaction was tolerant of a large variety of primary amides containing aryl, alkyl, and cinnamyl groups. A possible reaction mechanism for product formation was proposed.
- Zhang, Xiao-Feng,Li, Fa-Bao,Shi, Ji-Long,Wu, Jun,Liu, Li
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p. 1626 - 1632
(2016/02/19)
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- Nickel-Catalyzed Reductive Addition of Aryl/Benzyl Halides and Pseudohalides to Carbodiimides for the Synthesis of Amides
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A Nickel-catalyzed reductive process is described for the direct amidation of benzyl and aryl halides using carbodiimides as the amidating agent. Moreover, aryl and benzyl C–O electrophiles such as triflate, acetate, tosylate, trityl ether, and pivalate were converted into amides using this method. The in-situ-generated Ni0acts as a catalyst for the reaction at room temperature for benzylic substrates, and 70 °C for aryl electrophiles. This new nickel-catalyzed reductive coupling protocol provides a general and operationally simple method for the synthesis of diverse amides using carbodiimides. Amides bearing bulky substituents can be synthesized by this strategy in high yield, which demonstrates its effectiveness in amide synthesis.
- Panahi, Farhad,Jamedi, Fereshteh,Iranpoor, Nasser
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p. 780 - 788
(2017/01/18)
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- A method of from [...] amide
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The invention discloses a method for synthesizing amides from oxime. The method is characterized by adding oxime, water and a water-soluble iridium complex catalyst to a reaction vessel, cooling a reactant to the room temperature after the reaction mixture reacts at 80-120 DEG C for several hours, removing water through selective evaporation, and obtaining a target product through column separation. Compared with existing methods for synthesizing amides through oxime rearrangement in water through transition metal catalysis, the method has the advantages that the used catalyst is low in load and does not contain phosphine ligands severely polluting the environment, so that the reaction can be carried out in the air, without nitrogen protection; therefore the reaction meets the green chemical requirements and has an extensive development prospect.
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Paragraph 0108-0112
(2017/01/31)
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- Synthesis of Nitriles from Aldoximes and Primary Amides Using XtalFluor-E
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The dehydration reaction of aldoximes and amides for the synthesis of nitriles using [Et2NSF2]BF4 (XtalFluor-E) is described. Overall, the reaction proceeds rapidly (normally 1 h) at room temperature in an environmentally benign solvent (EtOAc) with only a slight excess of the dehydrating agent (1.1 equiv). A broad scope of nitriles can be prepared, including chiral nonracemic ones. In addition, in a number of cases, further purification of the nitrile after the workup was not required.
- Keita, Massaba,Vandamme, Mathilde,Paquin, Jean-Fran?ois
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p. 3758 - 3766
(2015/11/28)
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