- Fatty acid methyl esters into nitriles: Acid-base properties for enhanced catalysts
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Fatty nitriles have lately become of interest in the frame of biofuels or for the valorization of the oil part of biomass as fine chemicals such as polymers. The production of long-chain fatty nitriles by direct reaction of esters with ammonia has however not been academically extensively studied, although several catalysts were developed and published in patents. Acid-base features are implicitly considered as leading the catalysis of this reaction, but no direct correlation was investigated with any nature or number of acidic or basic sites. The present study aims at understanding which sites are responsible of this reaction and thus how to design better catalysts. Strong acidity correlates at 300 C for ester conversion and nitrile yield, suggesting a common nature of the reaction among all kinds of catalysts. An upper strength limit, over which undesirable side-products appear, was evaluated, and the factors influencing the production of N-methyl amide were analyzed.
- Mekki-Berrada,Bennici,Gillet,Couturier,Dubois,Auroux
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Read Online
- Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
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The synthesis of nitrile under mild conditions was achieved via dehydration of primary amide using lead salts as catalyst. The reaction processes were intensified by not only adding surfactant but also continuously removing the only by-product, water from the system. Both aliphatic and aromatic nitriles can be prepared in this manner with moderate to excellent yields. The reaction mechanisms were obtained with high-level quantum chemical calculations, and the crucial role the anionic ligand plays in the transformations were revealed.
- Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
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- Iodine Promoted Conversion of Esters to Nitriles and Ketones under Metal-Free Conditions
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We report a novel strategy to prepare valuable nitriles and ketones through the conversion of esters under metal-free conditions. By using the I2/PCl3 system, various substrates including aliphatic and aromatic esters could react with acetonitrile and arenes to afford the desired products in good to excellent yields. This method is compatible with a number of functional groups and provides a simple and practical approach for the synthesis of nitrile compounds and aryl ketones.
- Xiao, Jing,Guo, Fengzhe,Li, Yinfeng,Li, Fangshao,Li, Qiang,Tang, Zi-Long
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p. 2028 - 2035
(2021/02/03)
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- A Molecular Iron-Based System for Divergent Bond Activation: Controlling the Reactivity of Aldehydes
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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)
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- Method for continuous preparation of nitriles by amides (by machine translation)
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The method comprises the following steps: preparing a lead salt supported by a molecular sieve by a lead salt and a molecular sieve through an impregnation method; and filling a molecular sieve-loaded lead catalyst into a fixed bed reactor. The amide or amide solution is sent into a fixed bed reactor from the top of the fixed bed to be subjected to catalytic dehydration, and the obtained reaction product is led out from the bottom of the fixed bed. The reaction product is separated to obtain the crude product of the nitrile corresponding to the amide. A fixed bed continuous production process is adopted, the reaction process is simple, the production efficiency is high, the product post-treatment is simple, and industrial production is easy to realize. (by machine translation)
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Paragraph 0033-0054; 0061-0066
(2020/12/15)
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- Synthesis, characterization, catalytic and biological application of half-sandwich ruthenium complexes bearing hemilabile (κ2-: C, S)-thioether-functionalised NHC ligands
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A series of cationic Ru(ii)(η6-p-cymene) complexes with thioether-functionalised N-heterocyclic carbene ligands have been prepared and fully characterized. Steric and electronic influence of the R thioether substituent on the coordination of the sulfur atom was investigated. The molecular structure of three of them has been determined by means of X-ray diffractrometry and confirmed the bidentate (κ2-C,S) coordination mode of the ligand. Interestingly, only a single diastereomer, as an enantiomeric couple, was observed in the solid state for complexes 1c, 1i and 1j. DFT calculations established a low energy inversion barrier between the two diastereomers through a sulfur pyramidal inversion pathway with R donating group while a dissociative/associative mechanism is more likely with R substituents that contain electron withdrawing group, thus suggesting that the only species observed by the 1H-NMR correspond to an average resonance position of a fluxional mixtures of isomers. All these complexes were found to catalyse the oxydant-free double dehydrogenation of primary amine into nitrile. Ru complex bearing NHC-functionalised S-tBu group was further investigated in a wide range of amines and was found more selective for alkyl amine substrates than for benzylamine derivatives. Finally, preliminary results of the biological effects on various human cancer cells of four selected Ru complexes are reported.
- Achard, Thierry,Bellemin-Laponnaz, Stéphane,Chen, Weiguang,Egly, Julien,Maisse-Francois, Aline,Poblador-Bahamonde, Amalia I.
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supporting information
p. 3243 - 3252
(2020/03/19)
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- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
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We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
- Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
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p. 378 - 385
(2020/10/02)
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- Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
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The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.
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Paragraph 0034-0039; 0249-0254
(2020/09/16)
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- Dehydrogenation of Primary Alkyl Azides to Nitriles Catalyzed by Pincer Iridium/Ruthenium Complexes
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Pincer metal complexes exhibit superior catalytic activity in the dehydrogenation of plain alkanes, but find limited application in the dehydrogenation of functionalized organic molecules. Starting from easily accessible primary alkyl azides, here we report an efficient dehydrogenation of azides to nitriles using pincer iridium or ruthenium complexes as the catalysts. This method offers a route to cyanide-free preparation of nitriles without carbon chain elongation and without the use of strong oxidants. Both benzyl and linear aliphatic azides can be dehydrogenated with tert-butylethylene as the hydrogen acceptor to afford nitriles in moderate to high yields. Various functional groups can be tolerated, and the H?C?C?H bond dehydrogenation does not occur for linear alkyl azide substrates. Furthermore, the pincer Ir catalytic system was found to catalyze the direct azide dehydrogenation without the use of a sacrificial hydrogen acceptor.
- Gan, Lan,Jia, Xiangqing,Fang, Huaquan,Liu, Guixia,Huang, Zheng
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p. 3661 - 3665
(2020/06/02)
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- Tuning of active sites in M/TiO2 for photocatalytic cyanation of olefins with high regioselectivity
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The detailed structure of active sites plays an important role for the determination of catalytic performance. Herein, catalytic active sites of M/TiO2 for photocatalytic cyanation of olefins are tuned by delicate manipulation of the metal kinds, metal loading amount and pretreatment processes. It was found that the 0.1% Pt/P25 catalyst reduced at 300 °C possessed high metal dispersion and suitable oxygen defects on TiO2, and thus exhibited the best catalytic performance with high specific speed of time yield and high selectivity. A wide scope of olefin substrates could be converted to the corresponding nitriles with high atom efficiency and anti-Markovnikov regioselectivity under mild conditions for the optimized Pt/P25 catalyst. The reaction mechanism based on radical coupling of acetonitrile and olefins was also discussed. This approach offers an environmental-friendly platform for the selective activation of C-H bonds of acetonitrile and will bring potential applications for hydrofunctionalization of olefins.
- Bao, Jingxian,Huang, Min,Sun, Yuhan,Wu, Bo,Zhang, Shuyi,Zhong, Liangshu
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- Selective Transformations of Triglycerides into Fatty Amines, Amides, and Nitriles by using Heterogeneous Catalysis
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The use of triglycerides as an important class of biomass is an effective strategy to realize a more sustainable society. Herein, three heterogeneous catalytic methods are reported for the selective one-pot transformation of triglycerides into value-added chemicals: i) the reductive amination of triglycerides into fatty amines with aqueous NH3 under H2 promoted by ZrO2-supported Pt clusters; ii) the amidation of triglycerides under gaseous NH3 catalyzed by high-silica H-beta (Hβ) zeolite at 180 °C; iii) the Hβ-promoted synthesis of nitriles from triglycerides and gaseous NH3 at 220 °C. These methods are widely applicable to the transformation of various triglycerides (C4–C18 skeletons) into the corresponding amines, amides, and nitriles.
- Jamil, Md. A. R.,Siddiki, S. M. A. Hakim,Touchy, Abeda Sultana,Rashed, Md. Nurnobi,Poly, Sharmin Sultana,Jing, Yuan,Ting, Kah Wei,Toyao, Takashi,Maeno, Zen,Shimizu, Ken-ichi
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p. 3115 - 3125
(2019/04/26)
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- Ru@UiO-66(Ce) catalyzed acceptorless dehydrogenation of primary amines to nitriles: The roles of Lewis acid-base pairs in the reaction
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UiO-66(Ce)-encapsulated ruthenium nanoparticles (Ru@UiO-66(Ce)) was designed and used for dehydrogenation of primary amines to nitriles in water without any hydrogen acceptors and additives. Introduction of metal Ru to UiO-66(Ce) contributes to the formation of Lewis acid-base pairs on the catalyst owing to the metal-support interaction, acting as active sites for activation of amines and transfer of hydrogen. Ab initio calculation results further confirm the roles of Lewis acid-base pairs in the reaction.
- Lu, Guo-Ping,Li, Xinxin,Zhong, Lixiang,Li, Shuzhou,Chen, Fei
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supporting information
p. 5386 - 5393
(2019/10/11)
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- Easy Ruthenium-Catalysed Oxidation of Primary Amines to Nitriles under Oxidant-Free Conditions
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A dehydrogenation of primary amine to give the corresponding nitrile under oxidant- and base-free conditions catalysed by simple [Ru(p-cym)Cl2]2 with no extra ligand is reported. The system is highly selective for alkyl amines, whereas benzylamine derivatives gave the nitrile product together with the imine in a ratio ranging from 14:1 to 4:1 depending on the substrate. Preliminary mechanistic investigations have been performed to identify the key factors that govern the selectivity.
- Achard, Thierry,Egly, Julien,Sigrist, Michel,Maisse-Fran?ois, Aline,Bellemin-Laponnaz, Stéphane
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supporting information
p. 13271 - 13274
(2019/10/21)
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- Hydrofunctionalization of Olefins to Higher Aliphatic Alcohols via Visible-Light Photocatalytic Coupling
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Abstract: An atomically economical green protocol for the hydrofunctionalization of olefins to higher aliphatic alcohols with 100% anti-Markovnikov regioselectivity was developed via visible-light photocatalytic coupling. This method employs cheap, readily available and abundant methanol as both the C1 feedstock and the hydrogen source under visible light irradiation over CdS photocatalyst. A wide scope of olefin substrates could be hydrofunctionalized successfully to the corresponding higher alcohols with high selectivity. Besides alcohol, acetone and acetonitrile can also couple with olefins to generate the corresponding hydrofunctionalization products, suggesting promising potential industrial application. Graphical Abstract: [Figure not available: see fulltext.] Hydrofunctionalization of olefins to value-added chemicals with high selectivity was achieved via visible-light photocatalytic cross-coupling.
- Bao, Jingxian,Fan, Yonghui,Zhang, Shuyi,Zhong, Liangshu,Wu, Minghong,Sun, Yuhan
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- Enzymatic Synthesis of Aliphatic Nitriles at a Substrate Loading of up to 1.4 kg/L: A Biocatalytic Record Achieved with a Heme Protein
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A biocatalytic approach toward linear aliphatic nitriles being widely used as industrial bulk chemicals has been developed that runs at high substrate loadings of up to 1.4 kg/L as demonstrated for the synthesis of n-octanenitrile. This substrate loading is one of the highest ever reported in biocatalysis and to best of our knowledge the highest obtained for a water-immiscible product in aqueous medium. It is noteworthy that the biotransformation at such a high substrate loading was achieved by means of a metalloprotein bearing an iron-containing heme subunit in the active site. In detail, an aldoxime dehydratase from Bacillus sp. OxB-1 was used as a biocatalyst for a dehydration of aldoximes as readily available starting materials due to their easy preparation from aliphatic aldehydes through spontaneous condensation with hydroxylamine as bulk chemical. Excellent conversions toward the nitriles in the two-phase system were achieved and the products are easily separated from the reaction mixture without the need for further purification. Aliphatic nitriles are used in industry as solvents and intermediates for the production of surfactants and life sciences products.
- Hinzmann, Alessa,Glinski, Sylvia,Worm, Marion,Gr?ger, Harald
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supporting information
p. 4867 - 4872
(2019/05/09)
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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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- Sulfuryl Fluoride Mediated Conversion of Aldehydes to Nitriles
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Aliphatic, aromatic, and heteroaromatic aldehydes were readily converted to corresponding nitriles in a one-pot reaction sequence with hydroxylamine and sulfuryl fluoride. The reaction proceeds at room temperature, does not require metal catalysts and special precautions, and produces nitriles in excellent yields. It is compatible with a variety of functional groups, can be performed in aqueous and organic solvents, and is readily scalable to multigram quantities. Mild conditions and high selectivity of the reaction enabled the construction of polyfunctional probes containing nitrile, alkyne, azide, and fluorosulfate groups for further orthogonal derivatization.
- Gurjar, Jitendra,Bater, Jorick,Fokin, Valery V.
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supporting information
p. 1906 - 1909
(2019/01/24)
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- Mechanistic Insight Facilitates Discovery of a Mild and Efficient Copper-Catalyzed Dehydration of Primary Amides to Nitriles Using Hydrosilanes
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Metal-catalyzed silylative dehydration of primary amides is an economical approach to the synthesis of nitriles. We report a copper-hydride(CuH)-catalyzed process that avoids a typically challenging 1,2-siloxane elimination step, thereby dramatically increasing the rate of the overall transformation relative to alternative metal-catalyzed systems. This new reaction proceeds at ambient temperature, tolerates a variety of metal-, acid-, or base-sensitive functional groups, and can be performed using a simple ligand, inexpensive siloxanes, and low catalyst loading.
- Liu, Richard Y.,Bae, Minwoo,Buchwald, Stephen L.
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supporting information
p. 1627 - 1631
(2018/02/17)
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- Corresponding amine nitrile and method of manufacturing thereof
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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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Paragraph 0153; 0154; 0155; 0156; 0157
(2018/05/07)
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- Method for preparing nitrile from amine through catalytic oxidation
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The invention provides a method for preparing nitrile from amine through catalytic oxidation. The method comprises the steps of under visible light irradiation, preparing a co-catalyst from copper salt and tri(2,2'-dipyridyl) by taking oxygen as an oxidizing agent and lithium t-butoxide as alkali, and carrying out catalytic oxidation on amine, so as to synthesize a nitrile compound. No ligand is added, and the nitrile compound can be prepared through the irradiation of visible light, so that the method is simple and feasible; the oxidizing agent in the method is wide in source, and oxygen hasno pollution to the environment; and reaction conditions are mild, and the yield is high. The method has important significances to the synthesis of drugs, dyes, pesticides and heterocyclic compounds.
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Paragraph 0027-0029
(2018/07/30)
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- Copper-Catalyzed Unstrained C-C Single Bond Cleavage of Acyclic Oxime Acetates Using Air: An Internal Oxidant-Triggered Strategy toward Nitriles and Ketones
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A copper-catalyzed aerobic oxidative C-C single bond cleavage of acyclic unstrained oxime acetates is reported, providing various aryl nitriles and ketones in good yields. Mechanistic studies indicate a radical procedure is involved in this transformation, and the oxygen atom in the ketone products is originated from O2 in the air. Oxime acetates as an internal oxidant have been proved to be an initiator, which may promote the discovery of novel protocol for C-C bond cleavage and dioxygen activation.
- Zhu, Chuanle,Chen, Fulin,Liu, Chi,Zeng, Hao,Yang, Zhiyi,Wu, Wanqing,Jiang, Huanfeng
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p. 14713 - 14722
(2018/12/14)
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- An effective preparation of both 1,3-diketones and nitriles from alkynones with oximes as hydroxide sources
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An effective phosphine-catalyzed protocol has been established for the syntheses of 1,3-diketones and nitriles from alkynones with oximes as hydroxide surrogates. This method features the use of a phosphine catalyst, compatibility with various functional groups and ambient temperature, which makes this approach very practical. A plausible mechanism was proposed.
- Chen, Pei,Zhang, Qian-Qian,Guo, Jia,Chen, Lu-Lu,Wang, Yan-Bo,Zhang, Xiao
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p. 6958 - 6966
(2018/10/02)
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- Hydrofunctionalization of olefins to value-added chemicals: Via photocatalytic coupling
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A green strategy was developed for the synthesis of various value-added chemicals using methanol, acetonitrile, acetic acid, acetone and ethyl acetate as the hydrogen source by coupling them with olefins over heterogeneous photocatalysts. A radical coupling mechanism was proposed for the hydrofunctionalization of olefins with methanol to higher aliphatic alcohols over the Pt/TiO2 catalyst as the model reaction. C-H bond cleavage and C-C bond formation between photogenerated radicals and terminal olefins were accomplished in a single reaction at high efficiency. Our approach is atomically economical with high anti-Markovnikov regioselectivity and promising application potential under mild reaction conditions.
- Fan, Yonghui,Li, Shenggang,Bao, Jingxian,Shi, Lei,Yang, Yanzhang,Yu, Fei,Gao, Peng,Wang, Hui,Zhong, Liangshu,Sun, Yuhan
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supporting information
p. 3450 - 3456
(2018/08/06)
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- Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides
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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.
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supporting information
p. 266 - 273
(2018/01/12)
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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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- Copper (II)-catalysed direct conversion of aldehydes into nitriles in acetonitrile
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A mild one-pot method for the direct conversion of aryl, heteroaryl and alkyl aldehydes into nitriles was achieved by forming the corresponding oximes in situ with NH2OH and allowing them to react with CuO and acetonitrile. Yields of the 13 nitriles prepared were moderate to very good (62–91%).
- Ma, Xiaoyun,Ao, Jun,Chen, Zhengjian,Liu, Yi
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p. 465 - 468
(2017/08/18)
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- A practical iodine-catalyzed oxidative conversion of aldehydes to nitriles
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A simple and efficient method for the direct synthesis of nitriles from aldehydes using ammonium acetate as the nitrogen source has been developed. The reactions were performed with iodine as the catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant under mild conditions. A variety of aromatic, heteroaromatic, aliphatic and allylic aldehydes could be converted into their corresponding nitriles in good to excellent yields.
- Fang, Chaojie,Li, Meichao,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Jin, Liqun,Shen, Zhenlu
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p. 1484 - 1489
(2017/01/21)
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- Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles
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Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98 % isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products.
- Lambert, Kyle M.,Bobbitt, James M.,Eldirany, Sherif A.,Kissane, Liam E.,Sheridan, Rose K.,Stempel, Zachary D.,Sternberg, Francis H.,Bailey, William F.
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supporting information
p. 5156 - 5159
(2016/04/09)
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- Graphene oxide as a metal-free catalyst for oxidation of primary amines to nitriles by hypochlorite
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Graphene oxide catalyzes oxidation by NaClO of primary benzyl and aliphatic amines to a product distribution comprising nitriles and imines. Nitriles are the sole product for long chain aliphatic amines. Spectroscopic characterization suggests that percarboxylic and perlactone groups could be the active sites of the process.
- Primo, Ana,Puche, Marta,Pavel, Octavian D.,Cojocaru, Bogdan,Tirsoaga, Alina,Parvulescu, Vasile,García, Hermenegildo
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p. 1839 - 1842
(2016/02/12)
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- Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion
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We describe the use of simple copper-salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations.
- Xu, Boran,Hartigan, Elizabeth M.,Feula, Giancarlo,Huang, Zheng,Lumb, Jean-Philip,Arndtsen, Bruce A.
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supporting information
p. 15802 - 15806
(2016/12/16)
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- Catalytic Hydrogen Production by Ruthenium Complexes from the Conversion of Primary Amines to Nitriles: Potential Application as a Liquid Organic Hydrogen Carrier
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The potential application of the primary amine/nitrile pair as a liquid organic hydrogen carrier (LOHC) has been evaluated. Ruthenium complexes of formula [(p-cym)Ru(NHC)Cl2] (NHC=N-heterocyclic carbene) catalyze the acceptorless dehydrogenation of primary amines to nitriles with the formation of molecular hydrogen. Notably, the reaction proceeds without any external additive, under air, and under mild reaction conditions. The catalytic properties of a ruthenium complex supported on the surface of graphene have been explored for reutilization purposes. The ruthenium-supported catalyst is active for at least 10 runs without any apparent loss of activity. The results obtained in terms of catalytic activity, stability, and recyclability are encouraging for the potential application of the amine/nitrile pair as a LOHC. The main challenge in the dehydrogenation of benzylamines is the selectivity control, such as avoiding the formation of imine byproducts due to transamination reactions. Herein, selectivity has been achieved by using long-chain primary amines such as dodecylamine. Mechanistic studies have been performed to rationalize the key factors involved in the activity and selectivity of the catalysts in the dehydrogenation of amines. The experimental results suggest that the catalyst resting state contains a coordinated amine.
- Ventura-Espinosa, David,Marzá-Beltrán, Aida,Mata, Jose A.
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p. 17758 - 17766
(2016/11/28)
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- Iron-catalyzed dehydration of aldoximes to nitriles requiring neither other reagents nor nitrile media
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The dehydration of aldoximes is an environmentally benign reaction affording the desired nitrile and water as a by-product. However, most of the reported catalytic dehydration reactions of aldoximes require a solvent containing nitrile to synthesize the corresponding nitrile compounds. Inspired by recent reports on the enzymatic synthesis under nitrile-free conditions, we here describe that a simple iron salt catalyzes the dehydration of aldoximes requiring neither other reagents nor nitrile media. Our method can be applied to the one-pot synthesis of nitiriles from aldehydes. Dehydration causes: The dehydration of aldoximes is an environmentally benign reaction affording the desired nitrile and water as a by-product. However, most of the reported catalytic dehydration reactions of aldoximes require a solvent containing nitrile to synthesize the corresponding nitrile compounds. Inspired by recent reports on the enzymatic synthesis under nitrile-free conditions, here a simple iron salt-catalyzed dehydration of aldoximes requiring neither other reagents nor nitrile media is reported.
- Hyodo, Kengo,Kitagawa, Saki,Yamazaki, Masayuki,Uchida, Kingo
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supporting information
p. 1348 - 1352
(2016/05/19)
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- Nanocrystalline CeO2 as a Highly Active and Selective Catalyst for the Dehydration of Aldoximes to Nitriles and One-Pot Synthesis of Amides and Esters
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The dehydration of aldoximes into nitriles has been performed in the presence of various metal oxides with different acid-base properties (Al2O3, TiO2, CeO2, MgO). The results showed that a nanocrystalline CeO2 was the most active catalyst. An in situ IR spectroscopy study supports a polar elimination mechanism in the dehydration of aldoxime on metal oxide catalysts, in which Lewis acid sites and basic sites are involved. The Lewis acid sites intervene in the adsorption of the oxime on the catalyst surface while surface base sites are responsible for the C1-H bond cleavage. Thus, the acid-base properties of nanocrystalline CeO2 are responsible for the high catalytic activity and selectivity. A variety of aldoximes including alkyl and cycloalkyl aldoximes have been dehydrated into the corresponding nitriles in good yields (80-97%) using nanosized ceria which moreover resulted in a stable and reusable catalyst. Additionally, it has been showed that a variety of pharmacologically important products such as picolinamide and picolinic acid alkyl ester derivatives can be obtained in good yields from 2-pyridinaldoxime in a one-pot process using the nanoceria as catalyst.
- Rapeyko, Anastasia,Climent, Maria J.,Corma, Avelino,Concepción, Patricia,Iborra, Sara
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p. 4564 - 4575
(2016/07/12)
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- Aliphatic nitrile catalytic oxidation synthesis method
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The invention discloses an aliphatic nitrile catalytic oxidation synthesis method. With aliphatic aldehyde serving as reaction substrate, 2, 2, 6, 6-tetramethylpiperidine-1-oxygen radical (TEMPO), alkali metal salt and tert-butyl nitrite (TBN) as catalysts, hexamethyl-disilazane (HMDS) as the nitrogen source and oxygen as an oxidizing agent, the reaction substrate is reacted in organic solvent at normal pressure at the temperature of 25-50 DEG C, and aftertreatment is performed after reaction to obtain the aliphatic nitrile. The method is easy and safe to operate, and environment cost is lowered.
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Paragraph 0020; 0025
(2016/10/17)
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- One-Step Synthesis of Nitriles from Acids, Esters and Amides Using DIBAL-H and Ammonium Chloride
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A convenient, one-step procedure is presented for the conversion of carboxylic acids or their derivatives (esters, lactones, amides) to nitriles with an aminoalane reagent prepared from diisobutylaluminum hydride (DIBAL-H) and ammonium chloride.
- Wojtkielewicz, Agnieszka,?otowski, Zenon,Morzycki, Jacek W.
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supporting information
p. 2288 - 2292
(2015/09/28)
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- Direct oxidation of amines to nitriles in the presence of ruthenium-terpyridyl complex immobilized on ILs/SILP
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The immobilization of a ruthenium complex (Ru2Cl4(az-tpy)2) within a range of supported ionic liquids ([C4C1im]Cl, [C4C1im][NTf2], [C6C1im]Cl, [C4C1pyrr]Br, [C4C1im]Br, [C4C1pyrr]Cl) dispersed silica (SILP) operates as an efficient heterogeneous catalyst in oxidation of long chain linear primary amines to corresponding nitriles. This reaction follows a "green" route using a cheap and easy to handles oxidant (oxygen or air). The conversion was found to be strongly influenced by the alkyl chain length of the amine substrate and the choice of oxidant. No condensation reaction was observed between the starting amines and the selectivity to nitrile is 100%. Moving from a composition of 20 atm N2/5 atm O2 to 5 atm N2/20 atm O2 led to enhancements in the conversion (n-alkylamines) and selectivity (benzonitrile) which have been correlated with an increase of the solubilized oxygen. This was further supported by using different inert gas (nitrogen, helium, argon)/oxygen mixtures indicating that the O2 solubility in the SILP system, has an important effect on conversions and TON in this reaction using SILP catalysts. Experiments performed in the presence of CO2 led to a different behaviour due to the formation of amine-CO2 adducts. The application of the Weisz-Prater criterion confirmed the absence of any diffusional constraints.
- Pavel, Octavian Dumitru,Goodrich, Peter,Cristian, Liliana,Coman, Simona M.,Parvulescu, Vasile I.,Hardacre, Christopher
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p. 2696 - 2704
(2015/07/22)
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- Access to nitriles from aldehydes mediated by an oxoammonium salt
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A scalable, high yielding, rapid route to access an array of nitriles from aldehydes mediated by an oxoammonium salt (4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) and hexamethyldisilazane (HMDS) as an ammonia surrogate has been developed. The reaction likely involves two distinct chemical transformations: reversible silyl-imine formation between HMDS and an aldehyde, followed by oxidation mediated by the oxoammonium salt and desilylation to furnish a nitrile. The spent oxidant can be easily recovered and used to regenerate the oxoammonium salt oxidant.
- Kelly, Christopher B.,Lambert, Kyle M.,Mercadante, Michael A.,Ovian, John M.,Bailey, William F.,Leadbeater, Nicholas E.
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supporting information
p. 4241 - 4245
(2015/04/14)
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- Borohydride-mediated radical addition reactions of organic iodides to electron-deficient alkenes
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Cyanoborohydrides are efficient reagents in the reductive addition reactions of alkyl iodides and electron-deficient olefins. In contrast to using tin reagents, the reaction took place chemoselectively at the carbon-iodine bond but not at the carbon-bromine or carbon-chlorine bond. The reaction system was successfully applied to three-component reactions, including radical carbonylation. The rate constant for the hydrogen abstraction of a primary alkyl radical from tetrabutylammonium cyanoborohydride was estimated to be 4 M-1 s-1 at 25 °C by a kinetic competition method. This value is 3 orders of magnitude smaller than that of tributyltin hydride.
- Kawamoto, Takuji,Uehara, Shohei,Hirao, Hidefumi,Fukuyama, Takahide,Matsubara, Hiroshi,Ryu, Ilhyong
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supporting information
p. 3999 - 4007
(2014/05/20)
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- Cu/nitroxyl-catalyzed aerobic oxidation of primary amines into nitriles at room temperature
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An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4′-tBu 2bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one-N-oxyl). The reactions exhibit excellent functional group compatibility and substrate scope and are effective with benzylic, allylic, and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction.
- Kim, Jinho,Stahl, Shannon S.
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p. 1652 - 1656
(2013/07/26)
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- Novel ruthenium-terpyridyl complex for direct oxidation of amines to nitriles
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High catalytic activity and selectivity has been demonstrated for the oxidation of both aliphatic and aromatic amines to nitriles under benign conditions with dioxygen or air using the Ru2Cl4(az-tpy) 2 complex. The conversion was found to be strongly influenced by the alkyl chain length of the reactant with shorter chain amines found to have lower conversions than those with longer chains. Importantly, by using the ruthenium terpyridine complex functionalized with azulenyl moiety at the 4 position of central pyridine core provided a much higher reactivity catalyst compared with a series of ruthenium terpyridine-based ligand complexes reported. Mechanistic studies using deuterated benzylamine demonstrated the importance of RuOH in this reaction.
- Cristian, Liliana,Nica, Simona,Pavel, Octavian D.,Mihailciuc, Constantin,Almasan, Valer,Coman, Simona M.,Hardacre, Christopher,Parvulescu, Vasile I.
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p. 2646 - 2653
(2013/09/24)
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- Conversion of aldoximes into nitriles catalyzed by simple transition metal salt of the fourth period in acetonitrile
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Conversion of aldoximes into nitriles catalyzed by simple transition metal catalysts, such as copper salts, nickel salts, cobalt salts, zinc salts, iron salts, and manganese salts in acetonitrile was investigated. All the metal salts display catalytic property in the conversion of aldoximes into nitriles and cupric acetate exhibits much higher activity than other catalysts. The corresponding amide was detected in almost all cases and acetonitrile was found to be involved in the conversion of aldoximes into nitriles.
- Ma, Xiao-Yun,He, Ying,Lu, Ting-Ting,Lu, Ming
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p. 2560 - 2564
(2013/03/28)
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- Facile transformation of esters to nitriles
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Various esters were efficiently converted into the corresponding nitriles in good yields by the treatment with sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), followed by treatment with molecular iodine in aq ammonia. The present one-pot method is very efficient and practical for the conversion of various aromatic and aliphatic esters into the corresponding nitriles.
- Suzuki, Yusuke,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 7956 - 7962
(2011/11/07)
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- Direct transformation of N,N-disubstituted amides and isopropyl esters to nitriles
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Various N,N-dimethyl amides, N-methoxy-N-methyl amides, and isopropyl esters were smoothly transformed into the corresponding nitriles in good to moderate yields by the treatment with diisobutylaluminium hydride, followed by treatment with molecular iodine in aq ammonia. The present reactions are novel one-pot and practical methods for the transformation of N,N-disubstituted amides and isopropyl esters into nitriles, through the formation of hemiaminal O-AlBu2 and hemiacetal O-AlBu2, respectively.
- Suzuki, Yusuke,Yoshino, Takumi,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 3809 - 3814
(2011/06/25)
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- Direct oxidative conversion of alcohols, aldehydes and amines into nitriles using hypervalent iodine(III) reagent
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An efficient, facile, and high-yielding procedure for the direct oxidative conversion of alcohols, aldehydes, and primary, secondary, and tertiary amines into the corresponding nitriles using the hypervalent iodine(III) reagent hydroxy(tosyloxy)iodobenzene in combination with ammonium acetate as a nitrogen source is reported. The oxidation proceeded in mixed solvent to afford nitriles in excellent yields and high selectivity even at room temperature. Selective oxidation of primary amines in the presence of secondary amines and tertiary amines was also achieved. A possible mechanism for the oxidation is proposed.
- Zhu, Chenjie,Sun, Chengguo,Wei, Yunyang
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supporting information; experimental part
p. 4235 - 4241
(2011/02/25)
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- A facile and efficient one-pot synthesis of nitriles from aldehydes using hypervalent iodine(III) reagents in aqueous ammonium acetate
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A facile procedure for the direct oxidation of aldehydes to the corresponding nitriles using either the hypervalent iodine(III) reagent PhI(OAc)2 or a polymer-supported hypervalent iodine(III) reagent poly{4-[bis(acetoxy)iodo]}styrene as oxidant is reported. The oxidation proceeded in water at 70C in the presence of sodium dodecylsulfate using ammonium acetate as nitrogen source. The reaction was complete in four hours for the oxidation of benzylic and allylic aldehydes, and gave more than 90% yield in most cases. For the oxidation of aliphatic aldehydes, moderate to excellent yields of nitriles were also obtained after prolonged reaction times. Georg Thieme Verlag Stuttgart - New York.
- Zhu, Chenjie,Ji, Lei,Wei, Yunyang
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supporting information; experimental part
p. 3121 - 3125
(2010/11/04)
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- A metal-free catalytic system for the oxidation of benzylic methylenes and primary amines under solvent-free conditions
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Iodine-pyridine-tert-butylhydroperoxide is developed as a green and efficient catalytic system for the oxidation of benzylic methylenes to ketones and primary amines to nitriles. The reaction conditions are quite mild and environmentally benign, no transition metals, organic solvents or hazard reagents being needed. The oxidation of benzylic methylenes gave the corresponding ketones in excellent yields with complete chemoselectivity, while the oxidation of primary amines was complete in several minutes, affording various nitriles in moderate to good yields.
- Zhang, Jintang,Wang, Zhentao,Wang, Ye,Wan, Changfeng,Zheng, Xiaoqi,Wang, Zhiyong
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scheme or table
p. 1973 - 1978
(2010/06/15)
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- Catalytic oxidative conversion of alcohols, aldehydes and amines into nitriles using KI/I2-TBHP system
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The oxidative conversion of alcohols, aldehydes and amines to give corresponding nitriles in excellent yields was easily achieved by the catalytic amount of KI or I2 in combination with TBHP as an external oxidant. This non-transition metal catalyst is cost effective and provides easy work-up and separation of the product.
- Rajender Reddy,Uma Maheswari,Venkateshwar,Prashanthi,Lakshmi Kantam
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supporting information; experimental part
p. 2050 - 2053
(2009/09/06)
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- Direct oxidative conversion of alkyl halides into nitriles with molecular iodine and 1,3-diiodo-5,5-dimethylhydantoin in aq ammonia
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Various benzylic halides were smoothly and directly converted into the corresponding aromatic nitriles in high yields using molecular iodine and 1,3-diiodo-5,5-dimethylhydantoin, respectively, in aq ammonia. Similarly, primary alkyl halides were also converted into corresponding nitriles in moderate to good yields using molecular iodine and 1,3-diiodo-5,5-dimethylhydantoin in aq ammonia, although a long reaction time was required. The present reaction is a new method for the preparation of aromatic nitriles from benzylic halides and a new method for the conversion of alkyl halides into corresponding nitriles with retention of the number of carbon atoms.
- Iida, Shinpei,Ohmura, Ryosuke,Togo, Hideo
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experimental part
p. 6257 - 6262
(2011/03/20)
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- A facile one-pot conversion of aldehydes into nitriles
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A facile one-pot synthesis of nitriles starting with aldehydes has been developed employing hydroxylamine hydrochloride in dimethylsulfoxide at 100C.
- Chill, Samuel T.,Mebane, Robert C.
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scheme or table
p. 3601 - 3606
(2009/12/04)
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- Hydrosilanes are not always reducing agents for carbonyl compounds but can also induce dehydration: A ruthenium-catalyzed conversion of primary amides to nitriles
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A practical procedure for production of nitriles is offered by the triruthenium carbonyl cluster catalyzed dehydration of primary carboxamides with hydrosilanes under neutral conditions. This is the first example that a transition-metal-catalyzed activation of Si-H bonds does not lead to the reduction of carbonyl compounds but to dehydration. Possible mechanisms for the dehydration is discussed on the basis of NMR spectroscopic detection of intermediary species. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Hanada, Shiori,Motoyama, Yukihiro,Nagashima, Hideo
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supporting information; experimental part
p. 4097 - 4100
(2009/04/10)
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