- 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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- A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
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A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
- Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
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supporting information
p. 3190 - 3194
(2019/05/21)
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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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- Double Dehydrogenation of Primary Amines to Nitriles by a Ruthenium Complex Featuring Pyrazole Functionality
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A ruthenium(II) complex bearing a naphthyridine-functionalized pyrazole ligand catalyzes oxidant-free and acceptorless selective double dehydrogenation of primary amines to nitriles at moderate temperature. The role of the proton-responsive entity on the ligand scaffold is demonstrated by control experiments, including the use of a N-methylated pyrazole analogue. DFT calculations reveal intricate hydride and proton transfers to achieve the overall elimination of 2 equiv of H2.
- Dutta, Indranil,Yadav, Sudhir,Sarbajna, Abir,De, Subhabrata,H?lscher, Markus,Leitner, Walter,Bera, Jitendra K.
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supporting information
p. 8662 - 8666
(2018/07/09)
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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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- 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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- 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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- 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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- One-pot transformation of carboxylic acids into nitriles
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A variety of aromatic and aliphatic carboxylic acids were smoothly converted into the corresponding nitriles in good yields in a one-pot procedure by treatment with ethyl iodide/K2CO3/18-crown-6, followed by sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), and finally treatment with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH), and aqueous ammonia. This method is useful for the conversion of various aromatic and aliphatic carboxylic acids into the corresponding nitriles in a one-pot procedure. A variety of aromatic and aliphatic carboxylic acids were smoothly converted into the corresponding nitriles in good yields in a one-pot procedure by treatment with ethyl iodide/K2CO3/18-crown-6, followed by sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), and finally treatment with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH), and aqueous ammonia. Copyright
- Miyagi, Kotaro,Moriyama, Katsuhiko,Togo, Hideo
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p. 5886 - 5892
(2013/09/23)
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- Radical addition to acrylonitrile via catalytic photochemical decarboxylation of aliphatic carboxylic acids
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Photoinduced electron transfer (PET)-promoted decarboxylation of aliphatic carboxylic acids using catalytic amounts of an arene and electron-acceptor (>2.5 mol %) was found to proceed efficiently to give adducts even when only 1 equiv of acrylonitrile was
- Yoshimi, Yasuharu,Washida, Sonoka,Okita, Yoshiki,Nishikawa, Keisuke,Maeda, Kousuke,Hayashi, Shota,Morita, Toshio
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supporting information
p. 4324 - 4326
(2013/07/26)
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- Fe5C2 nanoparticles: A facile bromide-induced synthesis and as an active phase for Fischer-Tropsch synthesis
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Iron carbide nanoparticles have long been considered to have great potential in new energy conversion, nanomagnets, and nanomedicines. However, the conventional relatively harsh synthetic conditions of iron carbide hindered its wide applications. In this
- Yang, Ce,Hou, Yanglong,Zhao, Huabo,Ma, Ding
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supporting information
p. 15814 - 15821,8
(2020/08/24)
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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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- Lizard epidermal gland secretions. II. Chemical characterization of the generation gland secretion of the sungazer, cordylus giganteus
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In lizards, the epidermal glands of the femoral and precloacal regions are involved in the production of semiochemicals. In addition to its femoral glands, the giant girdled lizard, or sungazer, Cordylus giganteus, which is endemic to South Africa, has generation glands as an additional potential source of semiochemicals. These epidermal glands are described as glandular scales that overlay the femoral glands and are included in the normal epidermal profile located in the femoral (thigh) and anterior antebrachial (fore-leg) regions of the male sungazer. GC-MS analysis of the generation gland secretions and the trimethylsilyl derivatives of some of the steroidal constituents was employed to identify 59 constituents, including alkenes, carboxylic acids, alcohols, ketones, aldehydes, esters, amides, nitriles, and steroids. The quantitative differences of the volatile constituents of the fore- and hind-leg generation glands were compared between individuals. This is the first report on the chemical composition of generation glandular material of lizards.
- Louw, Stefan,Burger, Ben V.,Le Roux, Maritha,Van Wyk, Johannes H.
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experimental part
p. 1364 - 1369
(2011/08/09)
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- An efficient oxidation of primary azides catalyzed by copper iodide: A convenient method for the synthesis of nitriles
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A wide range of primary azides have been efficiently oxidized by a catalytic amount of CuI and TBHP into their corresponding nitriles in aqueous solution. A variety of oxidizable functional groups were well tolerated under the reaction conditions, and oxidation of secondary azides furnished their corresponding ketones (see scheme; TBHP=tert-butyl hydroperoxide).
- Lamani, Manjunath,Prabhu, Kandikere Ramaiah
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supporting information; experimental part
p. 6622 - 6625
(2010/11/04)
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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, facile synthesis of acyl azides and nitriles from carboxylic acids using bis(2-methoxyethyl)aminosulfur trifluoride
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A mild, efficient, and practical method for the one-step synthesis of acyl azides from carboxylic acids using bis(2-methoxyethyl)aminosulfur trifluoride is described. The reaction was easily extended to the synthesis of the corresponding nitriles by the inclusion of phosphorous reagents. The method can be applied to the synthesis of optically active nitriles in high yields, and is compatible with fluorous phosphines.
- Kangani, Cyrous O.,Day, Billy W.,Kelley, David E.
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p. 5933 - 5937
(2008/02/10)
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- Total synthesis and structural verification of some novel branched alkanes with quaternary carbons isolated from diverse geological sources
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With a view to the authentication of an unusual series of branched alkanes with quaternary centers (BAQCs) isolated from geological samples, and whose structures rest on the interpretation of EI-mass spectral fragmentation patterns, the total synthesis of 3-ethyl-3-methylheptadecane, 3,3-dimethylheptadecane, 3,3,11,11-tetraethyltridecane, and 5,5,7,7- tetraethylundecane is described. The GC-MS data of the first two samples are identical with those of the isolates and confirm their structures. However, the GC-MS data of the two more highly branched structures do not match those of the geological isolates leading to the conclusion that these structures were erroneously assigned.
- Crich, David,Xu, Huadong,Kenig, Fabien
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p. 5016 - 5019
(2007/10/03)
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- Dehydrogenation of amines to nitriles in aqueous micelles
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An aqueous reaction medium, based on a surfactant solution of dimethyldodecylamine N-oxide (DDAO) has been developed for the oxidative dehydrogenation of primary amines using NiSO4 as catalyst and K 2S2O8 as oxidant. This reaction medium enhances the rate of the reaction relative to other media previously reported in the literature, which are also toxic. The reactions of various aliphatic and cyclic amines have been investigated and gave nitriles with yields of >90% in mild conditions. The aqueous surfactant solution and reagents were recycled for future use. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
- Biondini, Daniele,Brinchi, Lucia,Germani, Raimondo,Goracci, Laura,Savelli, Gianfranco
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p. 3060 - 3063
(2007/10/03)
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- Process for forming branched composition catalytically by carbon-hydrogen bond activation in a saturated moiety
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A branched composition can be formed by reacting a reagent containing a saturated hydrocarbon moiety in the presence of (a) a catalyst capable of activating a carbon-hydrogen bond therein and (b) a branching reagent having a moiety that binds to the carbon atom in the carbon-hydrogen bond upon extraction of the hydrogen atom from that carbon-hydrogen bond. Suitable catalysts are those that comprise a transition metal cation possessing multiple oxidation states that is embedded in an anion that is a transition metal oxide possessing a higher oxidation state for the metal therein than the metal in the cation.
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Page/Page column 4
(2008/06/13)
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- An improved one-pot conversion of aldehydes into nitriles under microwave irradiation using ammonium acetate
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Various aryl and alkyl aldehydes underwent prompt one-pot conversion into the corresponding nitriles in high yields by reacting with hydroxylamine hydrochloride under microwave irradiation in the presence of ammonium acetate as catalyst.
- Das,Ramesh,Madhusudhan
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p. 1599 - 1600
(2007/10/03)
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- An efficient one-pot synthesis of nitriles from carboxylic acids without solvent under microwave irradiation
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Nitriles were prepared from alkyl and aryl carboxylic acids in dry media conditions, under microwave irradiation. Heating of the carboxylic acid, urea and amidosulfonic acid adsorbed on alumina support in a microwave oven affords nitriles in 20-93% yields.
- Juncai, Feng,Bin, Liu,Yang, Lhi,Changchuan, Li
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p. 4545 - 4548
(2007/10/03)
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- Ahmad-Strong synthesis of 8-, 9-, and 10-pentadecynoic acids.
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Three pentadecynoic acids, with the triple bond in the 8-, 9-, and 10-positions, have been synthesized on a gram scale in over-all yield of 65% by refinements of the five-step Ahmad-Strong method; isolation of intermediates was shown to be unnecessary prior to purification of the acetylenic nitriles by column chromatography on silicic acid. The melting points of the pentadecynoic acids alternate regularly and widely with position of unsaturation, in marked contrast to behavior of the homologous octadecynoic acids described by Huber.
- Howton,Stein
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p. 631 - 635
(2007/10/05)
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