- Envirocat EPZG(R), a new catalyst for the conversion of aldoximes into nitriles
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The conversion of aldoximes into nitriles was carried out at 100°C in the absence of a solvent using Envirocat EPZG(R) as a new solid supported catalyst.
- Bandgar,Jagtap,Ghodeshwar,Wadgaonkar
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Read Online
- Electrochemical Oxidative C?H Cyanation of Quinoxalin-2(1H)-ones with TMSCN
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Both quinoxalin-2(1H)-ones and nitriles are valuable organic compounds, and it is an interesting task to introduce cyano into quinoxalin-2(1H)-ones. Herein a regioselective C?H cyanation of quinoxalin-2(1H)-ones was developed with a nucleophilic cyano source TMSCN under electrochemical oxidative conditions. This process allowed the synthesis of C3 cyanated quinoxalin-2(1H)-ones in moderate to excellent yields in the absence of transition-metal catalysts and organic hydroperoxides.
- Li, Yifan,Liu, Ping,Sun, Peipei,Tong, Jinwen,Zhan, Yanling
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supporting information
p. 2193 - 2197
(2021/07/22)
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- SO2F2-mediated oxidation of primary and tertiary amines with 30% aqueous H2O2 solution
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A highly efficient and selective oxidation of primary and tertiary amines employing SO2F2/H2O2/base system was described. Anilines were converted to the corresponding azoxybenzenes, while primary benzylamines were transformed into nitriles and secondary benzylamines were rearranged to amides. For tertiary amine substrates quinolines, isoquinolines and pyridines, their oxidation products were the corresponding N-oxides. The reaction conditions are very mild and just involve SO2F2, amines, 30% aqueous H2O2 solution, and inorganic base at room temperature. One unique advantage is that this oxidation system is just composed of inexpensive inorganic compounds without the use of any metal and organic compounds.
- Liao, Xudong,Zhou, Yi,Ai, Chengmei,Ye, Cuijiao,Chen, Guanghui,Yan, Zhaohua,Lin, Sen
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supporting information
(2021/11/01)
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- Method for converting aromatic aldehyde into aromatic nitrile by using sulfur powder promoted inorganic ammonium as nitrogen source (by machine translation)
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The invention discloses a method for converting aromatic aldehyde into aromatic nitrile. The method is conversion of high yield of aromatic aldehyde one-pot reaction of sulfur powder promoted inorganic ammonium as a nitrogen source into aromatic nitrile. The method has the advantages of no need of metal participation, no need of strong oxide, compatibility of reaction to air, easiness in amplification to a gram scale and the like, and overcomes the problems of harsh reaction conditions, complex operation, low functional group compatibility and the like in the prior art. (by machine translation)
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Paragraph 0046; 0047
(2020/09/12)
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- Zn-catalyzed cyanation of aryl iodides
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We report the first example of zinc-catalyzed cyanation of aryl iodides with formamide as the cyanogen source. The transformation was promoted by the bisphosphine Nixantphos ligand. Under optimized conditions, a variety of electron-donating and electron-withdrawing aryl iodides were converted into nitrile products in good to excellent yields. This approach is an exceedingly simple and benign method for the synthesis of aryl nitriles and is likely to proceed via a dinuclear Zn-concerted catalysis.
- Zhao, Lulu,Dong, Yanan,Xia, Qiangqiang,Bai, Jianfei,Li, Yuehui
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p. 6471 - 6477
(2020/06/08)
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- Organophotoredox assisted cyanation of bromoarenes: via silyl-radical-mediated bromine abstraction
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The insertion of a nitrile (-CN) group into arenes through the direct functionalization of the C(sp2)-Br bond is a challenging reaction. Herein, we report an organophotoredox method for the cyanation of aryl bromides using the organic photoredox catalyst 4CzIPN and tosyl cyanide (TsCN) as the nitrile source. A photogenerated silyl radical, via a single electron transfer (SET) mechanism, was employed to abstract bromine from aryl bromide to provide an aryl radical, which was concomitantly intercepted by TsCN to afford the aromatic nitrile. A range of substrates containing electron-donating and -withdrawing groups was demonstrated to undergo cyanation at room temperature in good yields.
- Shah, Sk. Sheriff,Shee, Maniklal,Singh, N. D. Pradeep
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supporting information
p. 4240 - 4243
(2020/04/22)
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- Nickel-Catalyzed Cyanation of Aryl Halides and Hydrocyanation of Alkynes via C-CN Bond Cleavage and Cyano Transfer
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We report nickel-catalyzed cyanation and hydrocyanation methods to prepare aryl nitriles and vinyl nitriles from aryl halides and alkynes, respectively. Using inexpensive and nontoxic 4-cyanopyridine N-oxide as the cyano shuttle, the methods provide an efficient approach to prepare aryl cyanides and vinyl nitriles under mild and operationally simple reaction conditions with a broad range of functional group tolerances. In hydrocyanation of alkynes, the method demonstrated good regioselectivity, producing predominantly E- or Z-alkenyl nitriles in a controlled manner and exclusively Markovnikov vinyl nitriles when internal diaryl alkynes and terminal alkynes were applied as the substrates, respectively. The preliminary mechanistic investigation indicated that the C-CN bond cleavage process is promoted by oxidative addition to the nickel(I) complex in the cyanation of aryl halides, and further studies via a series of deuterium exchange experiments indicated that water serves as the hydrogen source for the hydrocyanation of alkynes.
- Chen, Hui,Sun, Shuhao,Liu, Yahu A.,Liao, Xuebin
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p. 1397 - 1405
(2020/02/04)
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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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- Photocatalytic Conversion of Benzyl Alcohols/Methyl Arenes to Aryl Nitriles via H-Abstraction by Azide Radical
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This report presents the visible-light-assisted synthesis of aryl nitriles from easily accessible alcohols or methyl arenes in the presence of O2. Organic photoredox catalyst, 4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene), induces single electron transfer (SET) from azide N3? and generates azide radical N3?.The photogenerated N3? abstracts H atom from α-C?H bond of benzylic system, which provides aldehyde and hydrazoic acid (HN3) in situ. This reaction subsequently forms azido alcohol intermediate that transforms into nitrile with the assistance of triflic acid (Br?nsted acid). A range of alcohols and methyl arenes successfully underwent cyanation at room temperature with good to excellent yields and showed good functional group tolerance.
- Shee, Maniklal,Shah, Sk. Sheriff,Singh, N. D. Pradeep
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supporting information
p. 14070 - 14074
(2020/10/12)
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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; 0190-0195
(2020/09/16)
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- Visible-light-driven catalytic oxidation of aldehydes and alcohols to nitriles by 4-acetamido-tempo using ammonium carbamate as a nitrogen source
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A mild and efficient route to prepare nitriles from aldehydes by combining photoredox catalysis with oxoammonium cations is reported. The reaction is performed using ammonium carbamate as the nitrogen source. The practicality of the method is increased by the extension of the dual catalytic system to one-pot two-step conversion of alcohols to nitriles.
- Nandi, Jyoti,Leadbeater, Nicholas E.
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supporting information
p. 9182 - 9186
(2019/11/05)
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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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- Organic semiconductor photocatalyst can bifunctionalize arenes and heteroarenes
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Photoexcited electron-hole pairs on a semiconductor surface can engage in redox reactions with two different substrates. Similar to conventional electrosynthesis, the primary redox intermediates afford only separate oxidized and reduced products or, more rarely, combine to one addition product. Here, we report that a stable organic semiconductor material, mesoporous graphitic carbon nitride (mpg-CN), can act as a visible-light photoredox catalyst to orchestrate oxidative and reductive interfacial electron transfers to two different substrates in a two- or three-component system for direct twofold carbon–hydrogen functionalization of arenes and heteroarenes. The mpg-CN catalyst tolerates reactive radicals and strong nucleophiles, is straightforwardly recoverable by simple centrifugation of reaction mixtures, and is reusable for at least four catalytic transformations with conserved activity.
- Ghosh, Indrajit,Khamrai, Jagadish,Savateev, Aleksandr,Shlapakov, Nikita,Antonietti, Markus,K?nig, Burkhard
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p. 360 - 366
(2019/08/15)
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- Ag/Cu-mediated decarboxylative cyanation of aryl carboxylic acids with K4Fe(CN)6 under aerobic conditions
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A method for facile synthesis of aryl nitriles has been well established via Ag/Cu-mediated decarboxylative cyanation of benzoic acids with K4Fe(CN)6 under aerobic conditions. The approach of using readily accessible aryl carboxylic acids and green K4Fe(CN)6 as starting material provides a feasible alternative to previous cyanation protocols. Control experiments revealed the key role of Cu for the process and excluded the possibility of a radical mechanism for the transformation.
- Fu, Zhengjiang,Jiang, Ligao,Li, Zhaojie,Jiang, Yongqing,Cai, Hu
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supporting information
p. 917 - 924
(2019/03/17)
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- Ligand-Promoted Non-Directed C?H Cyanation of Arenes
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This article reports the first example of a 2-pyridone accelerated non-directed C?H cyanation with an arene as the limiting reagent. This protocol is compatible with a broad scope of arenes, including advanced intermediates, drug molecules, and natural products. A kinetic isotope experiment (kH/kD=4.40) indicates that the C?H bond cleavage is the rate-limiting step. Also, the reaction is readily scalable, further showcasing the synthetic utility of this method.
- Liu, Luo-Yan,Yeung, Kap-Sun,Yu, Jin-Quan
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supporting information
p. 2199 - 2202
(2019/01/24)
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- Catalytic Cyanation Using CO2 and NH3
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Li and co-workers describe the catalytic cyanation of organic halides with CO2 and NH3. In the presence of Cu2O/DABCO as the catalyst, a variety of aromatic bromides and iodides were transformed to the desired nitrile products with broad functional-group tolerance. Both 13C- and/or 15N-labeled nitriles were obtained conveniently with appropriately isotope-labeled CO2 and NH3. Construction of functionalized chemical compounds from small molecules in a highly selective and efficient manner is crucial for sustainable development. The chemical-based manufacturing sector of the future should aim to produce chemicals from very simple and abundant resources, just as nature uses CO2 and N2 to generate sugars, amino acids, and so forth. In practice, however, the utilization of CO2 for the generation of industrial products, such as drugs and related intermediates, still remains a major challenge. Here, we describe the facile cyanide-free production of high-value nitriles with CO2 and NH3 as the sole sources of carbon and nitrogen, respectively. This practical and catalytic methodology provides a unique strategy for the utilization of small molecules for sustainable and cost-effective applications. Selective cyanation of aryl halides was achieved with CO2 and NH3 as the only sources of carbon and nitrogen, respectively. In the presence of Cu catalysts under low pressure (3 atm), a variety of aromatic iodides and bromides were transformed to the desired nitrile products without the use of toxic metal cyanides. Notably, olefins, esters, amides, alcohols, and amino groups were tolerated. Mechanistic studies suggest that Cu(III)-aryl insertion by isocyanate intermediates is involved. [13C,15N]-labeled nitriles were conveniently accessible from the respective isotope-labeled CO2 and NH3 via this methodology.
- Wang, Hua,Dong, Yanan,Zheng, Chaonan,Sandoval, Christian A.,Wang, Xue,Makha, Mohamed,Li, Yuehui
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supporting information
p. 2883 - 2893
(2019/01/05)
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- Electrochemical C-H cyanation of electron-rich (Hetero)arenes
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A straightforward method for the electrochemical C-H cyanation of arenes and heteroarenes that proceeds at room temperature in MeOH, with NaCN as the reagent in a simple, open, undivided electrochemical cell is reported. The platinum electrodes are passivated by ad-sorbed cyanide, which allows conversion of an exceptionally broad range of electron-rich substrates all the way down to dialkyl arenes. The cyanide electrolyte can be replenished with HCN, opening opportunities for salt-free industrial C-H cyanation.
- Hayrapetyan, Davit,Rit, Raja K.,Kratz, Markus,Tschulik, Kristina,Goo?en, Lukas J.
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supporting information
p. 11288 - 11291
(2018/10/20)
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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 0024-0026
(2018/07/30)
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- Catalyst-free, efficient and one pot protocol for synthesis of nitriles from aldehydes using glycerol as green solvent
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We described herein the novel, efficient and one-pot catalyst free protocol for the synthesis of nitriles from aldehydes by using hydroxyl amine hydrochlorides in glycerol as a green solvent. This protocol was efficiently used for transformation of aromatic aldehydes bearing electron-withdrawing and electron-donating groups into a aryl nitriles in good to excellent yields. The methodology offers a very simple, efficient and environmentally benign procedure.
- Ingale, Ajit P.,Patil, Shripad M.,Shinde, Sandeep V.
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p. 4845 - 4848
(2017/11/30)
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- Development of Decarboxylative Cyanation Reactions for C-13/C-14 Carboxylic Acid Labeling Using an Electrophilic Cyanating Reagent
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Degradation-reconstruction approaches for isotope labeling synthesis have been known for their remarkable efficiency, but applications are scarce due to some fundamental limitations of the chemistries developed to date. The decarboxylative cyanation reaction, as a degradation-reconstruction approach, is especially useful in rapid carboxylic acid carbon isotope labeling, however development toward its application as a widespread technique has stalled at the early stages due to numerous limitations which include somewhat narrow applicability. Employing the electrophilic cyanating reagent N-cyano-N-phenyl-p-toluenesulfonamide (NCTS) as the cyano source, efficient decarboxylative cyanation chemistry has been developed for aryl and alkyl carboxylic acids respectively with two rationally designed reaction pathways. The reactions provided good yields of nitrile products from carboxylic acids, with complete retention of isotopic purity from the [13CN]-NCTS used. The reaction conditions are relatively mild requiring no oxidant and no excess toxic heavy metal and the reagent [13/14CN]-NCTS is a stable, easy-to-handle crystalline solid that can be prepared quickly and effectively from the readily available [13/14C]-KCN. The following work describes this novel and efficient method for alkyl and aryl carboxylic acid isotopic labeling using a single reagent.
- Song, Fengbin,Salter, Rhys,Chen, Lu
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p. 3530 - 3537
(2017/04/11)
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- Direct C-H Cyanation of Arenes via Organic Photoredox Catalysis
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Methods for the direct C-H functionalization of aromatic compounds are in demand for a variety of applications, including the synthesis of agrochemicals, pharmaceuticals, and materials. Herein, we disclose the construction of aromatic nitriles via direct C-H functionalization using an acridinium photoredox catalyst and trimethylsilyl cyanide under an aerobic atmosphere. The reaction proceeds at room temperature under mild conditions and has proven to be compatible with a variety of electron-donating and -withdrawing groups, halogens, and nitrogen- and oxygen-containing heterocycles, as well as aromatic-containing pharmaceutical agents.
- McManus, Joshua B.,Nicewicz, David A.
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supporting information
p. 2880 - 2883
(2017/03/11)
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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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- Green method for catalyzing alcohols and ammonia to prepare nitriles by using heterogeneous mesoporous cobalt catalyst
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The invention provides a novel green method for catalyzing alcohols and ammonia to prepare nitriles by using a heterogeneous mesoporous cobalt catalyst. According to the method, cobalt acetate and nitrogen-containing ligands are taken as precursors, the novel heterogeneous mesoporous cobalt catalyst is prepared through high-temperature calcinations by using a hard template agent method, and catalyzed synthesis of various nitriles is realized in non-halogen solvents, particularly synthesis of aromatic and heterocyclic nitriles can be realized. The catalytic system has the characteristics that the novel and high-efficiency mesoporous cobalt catalyst is used; safe and green oxygen serves as an oxidizing agent; extra aids do not need to be added; the reaction is easy to operate; particularly the synthesis of aromatic and heterocyclic nitriles can be efficiently realized, and the nitriles can be repeatedly recycled. The novel heterogeneous mesoporous cobalt catalyst is used in the invention and has excellent research and industrial application prospects.
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Paragraph 0052-0054
(2017/07/20)
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- Metal-free catalysis of nitrogen-doped nanocarbons for the ammoxidation of alcohols to nitriles
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Here meso-N/C-900 derived from polypyridyl ligand DAA has been developed as a metal-free catalyst, for the first time, exhibiting good performance in catalytic ammoxidation of alcohols to nitriles. Systematic characterization suggests that the accessible mesopores and the effective pyridinic/pyrrolic-N are responsible for the unprecedented performance.
- Shang, Sensen,Dai, Wen,Wang, Lianyue,Lv, Ying,Gao, Shuang
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p. 1048 - 1051
(2017/02/05)
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- SUBSTITUTED IMIDAZOLIUM SULFURANES AND THEIR USE
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The present invention refers to substituted imidazolium sulfuranes, the use thereof for the transfer of a -CN group or an alkyne group.
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Page/Page column 17; 18; 19
(2017/01/26)
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- Aerobic Copper-Promoted Radical-Type Cleavage of Coordinated Cyanide Anion: Nitrogen Transfer to Aldehydes to Form Nitriles
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We have disclosed for the first time the copper-promoted C≡N triple bond cleavage of coordinated cyanide anion under a dioxygen atmosphere, which enables a nitrogen transfer to various aldehydes. Mechanistic study of this unprecedented transformation suggests that the single electron-transfer process could be involved in the overall course. This protocol provides a new cleavage pattern for the cyanide ion and would eventually lead to a more useful synthetic pathway to nitriles from aldehydes.
- Wu, Qian,Luo, Yi,Lei, Aiwen,You, Jingsong
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supporting information
p. 2885 - 2888
(2016/03/19)
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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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- High catalytic activity of mesoporous Co-N/C catalysts for aerobic oxidative synthesis of nitriles
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A high-efficiency and atom-economic synthetic strategy for nitriles by aerobic ammoxidation of alcohols is developed using a novel mesoporous cobalt-coordinated nitrogen-doped carbon catalyst (meso-Co-N/C) fabricated from a cobalt-coordinating polymer, which manifests superior activity towards the target reaction. The catalytic system features a broad substrate scope for various benzylic, allylic as well as heterocyclic alcohols, providing good to excellent yields of the target products with high selectivities, albeit with 0.5 mol% Co catalyst loading. 11,11′-Bis(dipyrido[3,2-a:2′,3′-c]phenazinyl) (bidppz) with extreme thermostability is selected as a robust ligand bridge between cobalt ions, resulting in the homogeneous distribution of active sites at the atomic or subnanoscale level and high catalyst yield. Silica colloid or ordered mesoporous silica SBA-15 is employed to realize the mesoporous structure. The unprecedented performance of the meso-Co-N/C catalyst is attributed to its high Brunauer-Emmett-Teller (BET) surface area (up to 680 m2 g-1) with a well-controlled mesoporous structure and homogeneous distribution of active sites. Kinetic analysis demonstrates that the catalytic oxidation of benzyl alcohol to benzaldehyde is the turnover-limiting step and that the apparent activation energy for benzonitrile synthesis is 61.5 kJ mol-1 and cationic species are involved in the reaction.
- Shang, Sensen,Wang, Lianyue,Dai, Wen,Chen, Bo,Lv, Ying,Gao, Shuang
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p. 5746 - 5753
(2016/07/21)
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- The application of NCTS (N-cyano-N-phenyl-p-toluenesulfonamide) in palladium-catalyzed cyanation of arenediazonium tetrafluoroborates and aryl halides
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Using NCTS (N-cyano-N-phenyl-p-toluenesulfonamide) as an electrophilic cyanation reagent, palladium-catalyzed cyanation of arenediazonium tetrafluoroborates and aryl halides was achieved under mild conditions. The method allowed the effective synthesis of various aryl nitriles in suitable yields via a coupling reaction.
- Li, Jizhen,Xu, Wenbin,Ding, Junshuai,Lee, Kuo-Hsiung
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supporting information
p. 1205 - 1209
(2016/03/01)
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- Molecular modeling and snake venom phospholipase A2 inhibition by phenolic compounds: Structure-activity relationship
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In our earlier study, we have reported that a phenolic compound 2-hydroxy-4-methoxybenzaldehyde from Janakia arayalpatra root extract was active against Viper and Cobra envenomations. Based on the structure of this natural product, libraries of synthetic structurally variant phenolic compounds were studied through molecular docking on the venom protein. To validate the activity of eight selected compounds, we have tested them in in vivo and in vitro models. The compound 21 (2-hydroxy-3-methoxy benzaldehyde), 22 (2-hydroxy-4-methoxybenzaldehyde) and 35 (2-hydroxy-3-methoxybenzylalcohol) were found to be active against venom-induced pathophysiological changes. The compounds 20, 15 and 35 displayed maximum anti-hemorrhagic, anti-lethal and PLA2 inhibitory activity respectively. In terms of SAR, the presence of a formyl group in conjunction with a phenolic group was seen as a significant contributor towards increasing the antivenom activity. The above observations confirmed the anti-venom activity of the phenolic compounds which needs to be further investigated for the development of new anti-snake venom leads.
- Alam, Md. Iqbal,Alam, Mohammed A.,Alam, Ozair,Nargotra, Amit,Taneja, Subhash Chandra,Koul, Surrinder
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p. 209 - 219
(2016/03/22)
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- Perfluoroalkanosulfonyl fluoride: A useful reagent for dehydration of aldoximes to nitriles
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The reaction of a variety of aldoximes with perfluoroalkanosulfonyl fluoride in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in dichloromethane smoothly generated the corresponding nitriles in 70%-95% yields.
- Yan, Zhao-Hua,Tian, Huan,Zhao, Dong-Dong,Jin, Hong-Ai,Tian, Wei-Sheng
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- Acetonitrile as a cyanating reagent: Cu-catalyzed cyanation of arenes
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A novel approach to the Cu-catalyzed cyanation of simple arenes using acetonitrile as an attractive cyano source has been documented. The C-H functionalization of arenes without directing groups involves a sequential iodination/cyanation to give the desired aromatic nitriles in good yields. A highly efficient Cu/TEMPO system for acetonitrile C-CN bond cleavage has been discovered. TEMPO is used as a cheap oxidant and enables the reaction to be catalytic in copper. Moreover, TEMPOCH2CN 6 has been identified as the active cyanating agent and shows high reactivity for forming the -CN moiety.
- Zhu, Yamin,Zhao, Mengdi,Lu, Wenkui,Li, Linyi,Shen, Zengming
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supporting information
p. 2602 - 2605
(2015/06/16)
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- Facile one-pot transformation of arenes into aromatic nitriles under metal-cyanide-free conditions
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Electron-rich arenes bearing methyl or methoxy groups on the aromatic ring were treated with dichloromethyl methyl ether and ZnBr2, and then with molecular iodine and aq. ammonia to give the corresponding aromatic nitriles in good yields. Using this method, febuxostat was efficiently prepared from 4-bromophenol in four steps. The method can be used for the preparation of aromatic nitriles from arenes in one pot under metal-cyanide-free conditions. Various electron-rich arenes could be effectively converted into the corresponding aromatic nitriles in good yields, by treatment with ZnBr2 and dichloromethyl methyl ether, followed by reaction with molecular iodine and aq. ammonia.
- Tamura, Toshiyuki,Moriyama, Katsuhiko,Togo, Hideo
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p. 2023 - 2029
(2015/03/18)
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- Copper-mediated cyanation of indoles and electron-rich arenes using DMF as a single surrogate
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The copper-mediated cyanation of indoles with DMF as a single surrogate has been realized. This approach could be applied for the cyanation of some electron-rich arenes and aryl aldehydes as well. Aryl aldehydes were demonstrated to be the key intermediates in the cascade process of cyanation of indoles and electron-rich arenes.
- Zhang, Lianpeng,Lu, Ping,Wang, Yanguang
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p. 8322 - 8329
(2015/08/03)
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- Palladium-catalyzed decarboxylative cyanation of aromatic carboxylic acids using [13C] and [14C]-KCN
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The development of robust and straightforward methods to efficiently label aromatic moieties starting from simple and convenient radio-synthetic sources still represents a considerable challenge. In this report, a new palladium-catalyzed decarboxylative cyanation protocol has been described. This procedure utilizes [14C]-labeled potassium cyanide, one of the simplest and commercially available sources of carbon-14. Under the optimized reaction conditions, a series of [13C] and [14C]-aromatic nitriles were easily prepared (12-74% yield starting from potassium cyanide). The usefulness of this methodology is highlighted by a rare example of a formal two-step [12C]-[14C] carbon isotope exchange. The current synthetic approach may represent a promising alternative to traditional preparations of relevant building blocks such as labeled aromatic nitriles.
- Loreau, Olivier,Georgin, Dominique,Taran, Frédéric,Audisio, Davide
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p. 425 - 428
(2015/11/18)
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- Utility of Nitrogen Extrusion of Azido Complexes for the Synthesis of Nitriles, Benzoxazoles, and Benzisoxazoles
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The utility of the nitrogen extrusion reaction of azido complexes, generated in situ from the corresponding aldehydes or ketones with TMSN3 in the presence of ZrCl4 or TfOH, has been described. These azido complexes could undergo three different pathways, depending on the substrates. First, azido methanolate complexes or imine diazonium ions could lead to benzisoxazole products via an intramolecular nucleophilic substitution. Second, imine diazonium ions could also undergo either the elimination of proton to provide nitrile products in good to excellent yields or an aryl migration, followed by an intramolecular nucleophilic addition, to give benzoxazole products in good yields.
- Nimnual, Phongprapan,Tummatorn, Jumreang,Thongsornkleeb, Charnsak,Ruchirawat, Somsak
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p. 8657 - 8667
(2015/09/15)
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- Dihalo(imidazolium)sulfuranes: A Versatile Platform for the Synthesis of New Electrophilic Group-Transfer Reagents
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The syntheses of imidazolium thiocyanates and imidazolium thioalkynes from dihalo(imidazolium) sulfuranes are reported and their reactivities as CN+ and R-CC+ synthons evaluated, respectively. The easy and scalable preparation of these electrophilic reagents, their operationally simple handling, broad substrate scope, and functional group tolerance clearly illustrate the potential of these species to become a reference for the direct electrophilic cyanation and alkynylation of organic substrates.
- Talavera, Garazi,Pe?a, Javier,Alcarazo, Manuel
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supporting information
p. 8704 - 8707
(2015/07/27)
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- An efficient transformation of primary halides into nitriles through palladium-catalyzed hydrogen transfer reaction
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Two-step one-pot transformation of primary halides into corresponding nitriles is successfully achieved. Nucleophilic substitution of primary halides with sodium azide and subsequent palladium-catalyzed hydrogen transfer proceeds smoothly in the presence of sterically bulky ligand dicyclohexyl(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphine (XPhos) in acetone to produce nitriles in satisfactory to good yields. This journal is
- Zou, Tao,Yu, Xiaoqiang,Feng, Xiujuan,Bao, Ming
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supporting information
p. 10714 - 10717
(2015/06/30)
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- Catalytic cyanation of aryl iodides using DMF and ammonium bicarbonate as the combined source of cyanide: A dual role of copper catalysts
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Cu(ii)-catalyzed cyanation of aryl iodides has been developed using DMF and ammonium bicarbonate as the combined source of cyanide. It is assumed that copper is involved both in the generation of CN units from DMF-ammonia and in the cyanation of aryl halides. A range of electron-rich and fused (hetero)aryl iodides underwent cyanation resulting in moderate to good yields.
- Pawar, Amit B.,Chang, Sukbok
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supporting information
p. 448 - 450
(2014/01/06)
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- Silver-catalyzed nitrogenation of alkynes: A direct approach to nitriles through C≡C bond cleavage
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Three in one blow! A novel direct transformation of alkynes into nitriles by a silver-catalyzed nitrogenation reaction through C≡C bond cleavage has been developed. This research provides both a new application for alkynes in organic synthesis, and valuable mechanistic insights into nitrogenation chemistry. Copyright
- Shen, Tao,Wang, Teng,Qin, Chong,Jiao, Ning
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supporting information
p. 6677 - 6680
(2013/07/25)
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- Palladium-catalyzed cyanation of aryl halides with CuSCN
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A palladium-catalyzed cyanation of aryl halides and borons has been developed by employing cuprous thiocyanate as a safe cyanide source. This protocol avoids the use of a highly toxic cyanide source, providing aromatic nitriles in moderate to good yields with good functional tolerance.
- Zhang, Guo-Ying,Yu, Jin-Tao,Hu, Mao-Lin,Cheng, Jiang
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p. 2710 - 2714
(2013/05/08)
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- Practical one-pot conversion of aryl bromides and β-bromostyrenes into aromatic nitriles and cinnamonitriles
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Various aryl bromides were efficiently converted into the corresponding aromatic nitriles in good yields by the treatment with Mg turnings and subsequently DMF, followed by treatment with molecular iodine and aq NH 3. The same treatment of aryl bromides, which are weakly reactive to Mg turnings, with iPrMgCl·LiCl and subsequently DMF, followed by the treatment with molecular iodine and aq NH3 also afforded the corresponding aromatic nitriles in good yields. On the other hand, when N-formylpiperidine was used instead of DMF, p-substituted β-bromostyrenes were converted into the corresponding p-substituted cinnamonitriles, i.e., α,β-unsaturated nitriles, in good to moderate yields by the same procedure. The reactions were carried out by means of a simple experimental procedure and did not require any toxic metal cyanides or expensive rare metals. Therefore, the present reactions are practical and environmentally benign one-pot methods for the preparation of aromatic nitriles, cinnamonitriles, and aliphatic nitriles from aryl bromides, β-bromostyrenes, and alkyl bromides, respectively, through the formation of Grignard reagents and their DMF or N-formylpiperidine adducts.
- Ishii, Genki,Harigae, Ryo,Moriyama, Katsuhiko,Togo, Hideo
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p. 1462 - 1469
(2013/02/25)
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- An unexpected involvement of ethyl-2-cyano-2-(hydroxyimino) acetate cleaved product in the promotion of the synthesis of nitriles from aldoximes: A mechanistic perception
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While attempting to synthesize nitriles from aldoximes using O-sulfonate esters of oxyma [ethyl 2-cyano-2-(hydroxyimino)acetate], an unexpected involvement of oxyma cleaved product in promoting the synthesis of nitriles was observed. Such involvement of the oxyma cleaved product in the reaction mechanism, together with the usual anticipated pathway improved drastically the applicability of the method by reducing the time needed for the reaction to be completed over that of the sulfonyl chlorides. Other advantages of the present protocol are excellent yields in ambient and milder conditions.
- Dev, Dharm,Palakurthy, Nani Babu,Kumar, Nitesh,Mandal, Bhubaneswar
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supporting information
p. 4397 - 4400
(2013/07/26)
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- Practical one-pot transformation of electron-rich aromatics into aromatic nitriles with molecular iodine and aq NH3 using Vilsmeier-Haack reaction
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Various electron-rich aromatics could be efficiently transformed into the corresponding aromatic nitriles in good to moderate yields by treatment with DMF and POCl3, followed by the reaction with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH) in aq NH3. Some of less reactive aromatics, such as anisole, 1,2-dimethoxybenzene, 1,4-dimethoxybenzene, and mesityrene, could be also transformed into the corresponding aromatic nitriles in good to moderate yields using N-methylformanilide and O(POCl 2)2, followed by the reaction with molecular iodine in aq NH3. Moreover, propiophenone derivatives could be successfully transformed into the corresponding β-chlorocinnamonitriles by the reaction with DMF and POCl3, followed by the reaction with molecular iodine and aq NH3. These reactions are novel metal-free one-pot methods for the preparation of aromatic nitriles from electron-rich aromatics and β-chlorocinnamonitriles from propiophenones.
- Ushijima, Sousuke,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 4588 - 4595
(2012/07/27)
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- Copper-mediated sequential cyanation of aryl C-B and arene C-H bonds using ammonium iodide and DMF
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The cyanation of aromatic boronic acids, boronate esters, and borate salts was developed under copper-mediated oxidative conditions using ammonium iodide and DMF as the source of nitrogen and carbon atom of the cyano unit, respectively. The procedure was successfully extended to the cyanation of electron-rich benzenes, and regioselective introduction of a cyano group at the arene C-H bonds was also achieved. The observation that the reaction proceeds via a two-step process, initial iodination and then cyanation, led us to propose that ammonium iodide plays a dual role to provide iodide and nitrogen atom of the cyano moiety.
- Kim, Jinho,Choi, Jiho,Shin, Kwangmin,Chang, Sukbok
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supporting information; experimental part
p. 2528 - 2531
(2012/04/04)
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- Pd(OAc)2-catalyzed alkoxylation of arylnitriles via sp 2 C-H bond activation using cyano as the directing group
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A Pd(OAc)2-catalyzed ortho-alkoxylation of arylnitrile was described. Using cyano as a directing group, the aromatic C-H bond can be functionalized efficiently to generate ortho-alkoxylated arylnitrile derivatives with moderate yields. The opti
- Li, Wu,Sun, Peipei
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p. 8362 - 8366
(2013/01/15)
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- Per-6-amino-β-cyclodextrin/CuI catalysed cyanation of aryl halides with K4[Fe(CN)6]
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Efficient cyanation of aryl halides is achieved using less toxic K 4[Fe(CN)6] as the reagent and amino-β-cyclodextrins as supramolecular ligands for CuI. Four different amino cyclodextrins viz. per-6-amino-β-CD, per-6-methylamino-β-CD, per-6-butyl-amino-β-CD and mono-6-amino-β-CD are prepared and studied. Aryl and heteroaryl nitriles are obtained in good to excellent yield for even bromo derivatives of flavone and 2-aminopyrans. This system uses catalytic amounts (10 mol%) of both copper iodide and per-6-amino-β-cyclodextrin. Easy separation, the absence of nitrogen atmosphere and excellent yield are the other significant outcomes of this protocol. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
- Azath, Ismail Abulkalam,Suresh, Palaniswamy,Pitchumani, Kasi
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supporting information
p. 2334 - 2339
(2013/01/15)
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- Copper-catalyzed oxidative cyanation of aryl halides with nitriles involving carbon-carbon cleavage
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A novel, general route for the synthesis of aromatic nitriles is presented that proceeds through Cu(OAc)catalyzed oxidative cyanation of aryl halides using commercially available nitriles as the cyanide sources and Ag/air as the oxidizing agent. It is noteworthy that this work provides a new example of using acetonitrile as the cyanide source for aromatic nitrile synthesis through a Cu-catalyzed oxidative C-C bond cleavage and cyanation process.
- Song, Ren-Jie,Wu, Ji-Cheng,Liu, Yu,Deng, Guo-Bo,Wu, Cui-Yan,Wei, Wen-Ting,Li, Jin-Heng
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supporting information
p. 2491 - 2496,6
(2012/12/11)
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- Ethyl cyanoacetate: A new cyanating agent for the palladium-catalyzed cyanation of aryl halides
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A new Pd-catalyzed cyanation reaction has been discovered using ethyl cyanoacetate as the cyanating reagent. A variety of electron-rich and electron-deficient aryl halides were efficiently converted into their corresponding nitriles in good to excellent yields.
- Zheng, Shuyan,Yu, Chunhui,Shen, Zhengwu
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supporting information; experimental part
p. 3644 - 3647
(2012/08/28)
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- Practical synthesis of aromatic nitriles via gallium-catalysed electrophilic cyanation of aromatic C-H bonds
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A gallium-catalysed, direct cyanation reaction of aromatic and heteroaromatic C-H bonds with cyanogen bromide was developed as a practical synthetic method for the preparation of aromatic nitriles. The Royal Society of Chemistry 2012.
- Okamoto, Kazuhiro,Watanabe, Masahito,Murai, Masahito,Hatano, Ryo,Ohe, Kouichi
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supporting information; experimental part
p. 3127 - 3129
(2012/04/23)
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