- Increasing the scope of palladium-catalyzed cyanations of aryl chlorides
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An improved protocol for the palladium-catalyzed cyanation of electron-rich aryl chlorides with potassium ferrocyanide [K4[Fe(CN)6]] is presented. Compared to previous procedures the substrate scope is significantly broadened.
- Schareina, Thomas,Jackstell, Ralf,Schulz, Thomas,Zapf, Alexander,Cotte, Alain,Gotta, Matthias,Beller, Matthias
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Read Online
- Photocyanation of Anisole in the Presence of Polyethylene Glycol
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Polyethylene glycol can replace crown ether as a co-solvent in the photochemical substitution reaction of anisole with KCN in CH2Cl2.
- Suzuki, Nobutaka,Shimazu, Kazuo,Ito, Toshikuni,Izawa, Yasuji
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Read Online
- Synthesis of low molecular weight compounds with complement inhibition activity
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An attempt was made to synthesize a series of non-cytotoxic low molecular weight meta-substituted aromatic ethers (2-4, 5-7) and some of their bioisosteres (14-16) and to evaluate their activity on the activation of human complement (classical pathway) and their intrinsic hemolytic activity. The in vitro assay results of the inhibition of complement-mediated hemolysis by these analogues indicate that the aldehydic meta substituted aromatic ethers show inhibitory potency, while carboxylic acid meta substituted aromatic ethers show hemolytic activity. Some of the bioisosteres exhibit both inhibitory as well as hemolytic property.
- Master, Hoshang E.,Khan, Shabana I.,Poojari, Krishna A.
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Read Online
- Highly dispersed Co species in N-doped carbon enhanced the aldehydes ammoxidation reaction activity
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Developing environmentally friendly catalysts with high activity for the ammoxidation of aromatic aldehydes to aromatic nitriles is greatly important for this industrial transformation. Herein, natural vitamin B12 was used as a carbon source for the preparation of a cobalt- and nitrogen-doped catalyst precursor, which was pyrolyzed at different temperatures to obtain cobalt- and nitrogen-doped carbon (Co@NC-T) (T denotes pyrolysis temperature) catalysts. The Co@NC-800 exhibited excellent activity and selectivity in the ammoxidation of aromatic aldehydes with ammonium carbonate to aromatic nitriles compared to the Co@NC-700, Co@NC-600 and Co@NC-500 catalysts. The high catalytic performance of Co@NC-800 could be due to the presence of the low-density electron cloud of the highly dispersed Co species, which could interact with the benzene ring of benzaldehyde bearing p-π conjugate, thereby promoting the adsorption and activation of benzaldehyde. Consequently, the activated benzaldehyde reacted with amino groups that were decomposed from ammonium carbonate and subsequently underwent a dehydration process to form nitriles.
- Fu, Wenqian,Pan, Liuming,Tang, Tiandi,Wang, Siming,Zhang, Lei
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- Palladium-catalyzed synthesis of nitriles from N-phthaloyl hydrazones
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The Pd-catalyzed transformation of N-phthaloyl hydrazones into nitriles involving the cleavage of an N-N bond is reported. The use of N-heterocyclic carbene as a ligand is essential for the success of the reaction. N-Phthaloyl hydrazones prepared from aromatic aldehydes or cyclobutanones are applicable to this transformation, which gives aryl or alkenyl nitriles, respectively.
- Ano, Yusuke,Chatani, Naoto,Higashino, Masaya,Yamada, Yuki
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supporting information
p. 3799 - 3802
(2022/04/07)
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- Cyanide-Free Cyanation of Aryl Iodides with Nitromethane by Using an Amphiphilic Polymer-Supported Palladium Catalyst
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A cyanide-free aromatic cyanation was developed that uses nitromethane as a cyanide source in water with an amphiphilic polystyrene poly(ethylene glycol) resin-supported palladium catalyst and an alkyl halide (1-iodobutane). The cyanation proceeds through the palladium-catalyzed cross-coupling of an aryl halide with nitromethane, followed by transformation of the resultant (nitromethyl)arene intermediate into a nitrile by 1-iodobutane.
- Niimi, Ryoko,Suzuka, Toshimasa,Uozumi, Yasuhiro
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supporting information
p. 40 - 44
(2021/11/30)
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- Recyclable and Reusable Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O System for Cyanation of Aryl Chlorides with Potassium Ferrocyanide
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Pd(OAc)2/XPhos–SO3Na in a mixture of poly(ethylene glycol) (PEG-400) and water is shown to be a highly efficient catalyst for the cyanation of aryl chlorides with potassium ferrocyanide. The reaction proceeded smoothly at 100 or 120?oC with K2CO3 or KOAc as base, delivering a variety of aromatic nitriles in good to excellent yields. The isolation of the crude products is facilely performed by extraction with cyclohexane and more importantly, both expensive Pd(OAc)2 and XPhos–SO3Na in PEG-400/H2O system could be easily recycled and reused at least six times without any apparent loss of catalytic efficiency. Graphical Abstract: Palladium-catalyzed cyanation of aryl chlorides with potassium ferrocyanide leading to aryl nitriles by using Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O as a highly efficient and recyclable catalytic system is described.[Figure not available: see fulltext.]
- Cai, Mingzhong,Huang, Bin,Liu, Rong,Xu, Caifeng
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- One pot synthesis of aryl nitriles from aromatic aldehydes in a water environment
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In this study, we found a green method to obtain aryl nitriles from aromatic aldehyde in water. This simple process was modified from a conventional method. Compared with those approaches, we used water as the solvent instead of harmful chemical reagents. In this one-pot conversion, we got twenty-five aryl nitriles conveniently with pollution to the environment being minimized. Furthermore, we confirmed the reaction mechanism by capturing the intermediates, aldoximes.
- Chen, Qingqing,Han, Hongwei,Lin, Hongyan,Ma, Xiaopeng,Qi, Jinliang,Wang, Xiaoming,Yang, Yonghua,Zhou, Ziling
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p. 24232 - 24237
(2021/07/29)
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- 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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- A highly stable all-in-one photocatalyst for aryl etherification: The NiIIembedded covalent organic framework
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The efficient conversion of aryl bromides to the corresponding aryl alkyl ethers by dual nickel/photocatalysis has seen great progress, but difficulties of recycling the photosensitizer or nickel complexes cause problems of sustainability. Here, we report the design of a novel, highly stable vinyl bridge 2D covalent organic framework (COF) containing Ni, which combines the role of photosensitizer and reactive site. The as-prepared sp2c-COFdpy-Ni acts as an efficient heterogeneous photocatalyst for C-O cross coupling. The sp2c-COFdpy-Ni can be completely recovered and used repeatedly without loss of activity, overcoming the limitations of the prior methods. Preliminary studies reveal that strong interlayer electron transfer may facilitate the generation of the proposed intermediate sp2c-COFdpy-NiI in a bimolecular and self-sustained manner. This all-in-one heterogeneous photocatalyst exhibits good compatibility of substrates and tolerance of functional groups. The successful attempt to expand the 2D COFs with this new catalyst into photocatalytic organic transformation opens an avenue for photoredox/transition metal mediated coupling reactions.
- Chen, Hao,Dong, Wenbo,Hu, Jianxiang,Rao, Li,Wang, Pei,Wang, Shengyao,Xiang, Yonggang,Yang, Yi
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p. 5797 - 5805
(2021/08/23)
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- Copper-Catalyzed Methoxylation of Aryl Bromides with 9-BBN-OMe
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A Cu-catalyzed cross-coupling reaction between aryl bromides and 9-BBN-OMe to provide aryl methyl ethers under mild conditions is reported. The oxalamide ligand BHMPO plays a key role in the transformation. Various functional groups on bromobenzenes are well tolerated, providing the desired anisole products in moderate to high yields.
- Li, Chen,Song, Zhi-Qiang,Wang, Dong-Hui,Wang, Jing-Ru
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supporting information
p. 8450 - 8454
(2021/11/17)
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- Nickel-Catalyzed Hydrodeoxygenation of Aryl Sulfamates with Alcohols as Mild Reducing Agents
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The nickel-catalyzed hydrodeoxygenation of aryl sulfamates has been developed with alcohols as mild reductants. A variety of functional groups and heterocycles were tolerated in this reaction system to give the desired products in high yields. In addition, the gram-scale process and stepwise cine-substitution were also achieved with high efficiency.
- Matsuo, Kasumi,Kuriyama, Masami,Yamamoto, Kosuke,Demizu, Yosuke,Nishida, Koyo,Onomura, Osamu
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p. 4449 - 4460
(2021/08/25)
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- Discovery and characterization of a novel perylenephotoreductant for the activation of aryl halides
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To develop a photocatalyst with catalytical activity for substrates with low reactivities is always highly desired. Herein, based on the principle of structure–property relationships, we rationally designed the natural product cercosporin, the naturally occurring perylenequinonoid pigment, to develop a novel organic perylenephotoreductant, hexacetyl reduced cercosporin (HARCP), through structural manipulation. Compared with cercosporin, HARCP shows prominent electrochemical and photophysical characteristics with greatly improved photoreductive activity, fluorescence lifetime and fluorescence quantum yield. These properties allowed HARCP as a powerful photoreductant to efficiently realize a series of benchmark reactions, including photoreduction, alkoxylation and hydroxylation to construct C–H and C–O bonds using aryl halides as substrates under mild conditions, all of which have never been achieved by the same photocatalyst. Thus, this study well supports the notion that the principle between structural manipulation and photocatalytic activity is of great significance to design customized photocatalysts for photoredox chemistry.
- Guo, Baodang,Huang, Shuping,Li, Jia,Li, Min,Liu, Xuanzhong,Rao, Yijian,Wu, Yawen,Yin, Huimin,Yuan, Zhenbo,Zhang, Yan
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p. 111 - 120
(2021/06/16)
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- Copper-promoted cyanation of aryl iodides with N,N-dimethyl aminomalononitrile
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A copper-promoted cyanation of aryl iodides has been successfully developed by using N,N-dimethyl aminomalononitrile as the cyanide source with moderate toxicity and better stability. This reaction features broad substrate scope, excellent reaction yields, readily available catalyst, and simple reaction conditions.
- Liu, Si-Zhan,Li, Jing,Xue, Cao-Gen,Xu, Xue-Tao,Lei, Lin-Sheng,Huo, Chen-Yu,Wang, Zhen,Wang, Shao-Hua
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supporting information
(2021/02/01)
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- Pd@CeO2-catalyzed cyanation of aryl iodides with K4Fe(CN)6·3H2O under visible light irradiation
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Cyanation of aryl iodides is still challenging work for chemical researchers because of harsh reaction conditions and toxic cyanide sources. Herein, we have developed a new protocol based on the combination of the catalyst Pd@CeO2, nontoxic cyanide source K4[Fe (CN)6]·3H2O, and driving force visible light irradiation. The reaction is operated at relatively moderate temperature (55°C) and exhibits good catalytic efficiency of product aryl nitriles (yields of 89.4%). Moreover, the catalyst Pd@CeO2 possesses good reusability with a slight loss of photocatalytic activity after five consecutive runs. The reaction system based on the above combination shows a wide range of functional group tolerance under the same conditions. Reaction conditions such as temperature, time, the component of catalyst, and solutions are optimized by studying cyanation of 1-iodo-4-nitrobenzene as model reaction. According to these results, the possible mechanism of Pd@CeO2-catalyzed cyanation of aryl iodides under visible light irradiation is proposed based on the influence of visible light on the catalyst and reactant compounds. In all, we provided an environmental and economic method for preparation of aryl nitriles from cyanation of aryl iodides based on the goal of green chemistry for sustainable development.
- Wang, Shengyu,Wang, Jianqiang,Pan, Junyi,Liu, Cheng,Gong, Xubin,Guo, Cheng
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- Decarbonylative Synthesis of Aryl Nitriles from Aromatic Esters and Organocyanides by a Nickel Catalyst
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A decarbonylative cyanation of aromatic esters with aminoacetonitriles in the presence of a nickel catalyst was developed. The key to this reaction was the use of a thiophene-based diphosphine ligand, dcypt, permitting the synthesis of aryl nitrile without the generation of stoichiometric metal- or halogen-containing chemical wastes. A wide range of aromatic esters, including hetarenes and pharmaceutical molecules, can be converted into aryl nitriles.
- Iizumi, Keiichiro,Kurosawa, Miki B.,Isshiki, Ryota,Muto, Kei,Yamaguchi, Junichiro
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supporting information
p. 1555 - 1559
(2020/11/10)
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- Product selectivity controlled by manganese oxide crystals in catalytic ammoxidation
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The performances of heterogeneous catalysts can be effectively tuned by changing the catalyst structures. Here we report a controllable nitrile synthesis from alcohol ammoxidation, where the nitrile hydration side reaction could be efficiently prevented by changing the manganese oxide catalysts. α-Mn2O3 based catalysts are highly selective for nitrile synthesis, but MnO2-based catalysts including α, β, γ, and δ phases favour the amide production from tandem ammoxidation and hydration steps. Multiple structural, kinetic, and spectroscopic investigations reveal that water decomposition is hindered on α-Mn2O3, thus to switch off the nitrile hydration. In addition, the selectivity-control feature of manganese oxide catalysts is mainly related to their crystalline nature rather than oxide morphology, although the morphological issue is usually regarded as a crucial factor in many reactions.
- Hui, Yu,Luo, Qingsong,Qin, Yucai,Song, Lijuan,Wang, Hai,Wang, Liang,Xiao, Feng-Shou
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p. 2164 - 2172
(2021/09/20)
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- HCl·DMPU-assisted one-pot and metal-free conversion of aldehydes to nitriles
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We report an efficient HCl·DMPU assisted one-pot conversion of aldehydes into nitriles. The use of HCl·DMPU as both an acidic source as well as a non-nucleophilic base constitutes an environmentally mild alternative for the preparation of nitriles. Our protocol proceeds smoothly without the use of toxic reagents and metal catalysts. Diverse functionalized aromatic, aliphatic and allylic aldehydes incorporating various functional groups were successfully converted to nitriles in excellent to quantitative yields. This protocol is characterized by a broad substrate scope, mild reaction conditions, and high scalability. This journal is
- Hammond, Gerald B.,Mudshinge, Sagar R.,Potnis, Chinmay S.,Xu, Bo
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supporting information
p. 4161 - 4164
(2020/07/14)
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- Nitrile Synthesis by Aerobic Oxidation of Primary Amines and in situ Generated Imines from Aldehydes and Ammonium Salt with Grubbs Catalyst
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Herein, a Grubbs-catalyzed route for the synthesis of nitriles via the aerobic oxidation of primary amines is reported. This reaction accommodates a variety of substrates, including simple primary amines, sterically hindered β,β-disubstituted amines, allylamine, benzylamines, and α-amino esters. Reaction compatibility with various functionalities is also noted, particularly with alkenes, alkynes, halogens, esters, silyl ethers, and free hydroxyl groups. The nitriles were also synthesized via the oxidation of imines generated from aldehydes and NH4OAc in situ. (Figure presented.).
- Utsumi, Tatsuki,Noda, Kenta,Kawauchi, Daichi,Ueda, Hirofumi,Tokuyama, Hidetoshi
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supporting information
p. 3583 - 3588
(2020/08/05)
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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 0038; 0039
(2020/09/12)
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- Nickel-Catalyzed Transformation of Alkene-Tethered Oxime Ethers to Nitriles by a Traceless Directing Group Strategy
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Nickel-catalyzed transformation of alkene-tethered oxime ethers to nitriles using a traceless directing group strategy has been developed. A series of alkene-tethered oxime ethers derived from benzaldehyde and cinnamyl aldehyde derivatives were converted into the corresponding benzonitriles and cinnamonitriles in 46-98% yields using the nickel catalyst system. Control experiments showed that the alkene group tethered to an oxygen atom on the oximes via one methylene unit plays a key role as a traceless directing group during the catalysis.
- Takahashi, Yoshiyuki,Tsuji, Hiroaki,Kawatsura, Motoi
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p. 2654 - 2665
(2020/02/04)
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- An Efficient Synthesis of Nitriles from Aldoximes in the Presence of Trifluoromethanesulfonic Anhydride in Mild Conditions
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Abstract: A new and convenient protocol has been proposed for the transformation of aldoximes to nitriles using trifluoromethanesulfonic anhydride and triethylamine. The proposed method allows a range of aldoximes, including aromatic, heterocyclic, aliphatic, and cycloaliphatic aldoximes, to be converted to the corresponding nitriles in good to excellent yields.
- Uludag, N.
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p. 1640 - 1645
(2020/10/22)
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- NHC-catalyzed silylative dehydration of primary amides to nitriles at room temperature
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Herein we report an abnormal N-heterocyclic carbene catalyzed dehydration of primary amides in the presence of a silane. This process bypasses the energy demanding 1,2-siloxane elimination step usually required for metal/silane catalyzed reactions. A detailed mechanistic cycle of this process has been proposed based on experimental evidence along with computational study.
- Ahmed, Jasimuddin,Hota, Pradip Kumar,Maji, Subir,Mandal, Swadhin K.,Rajendran, N. M.
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supporting information
p. 575 - 578
(2020/01/29)
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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; 0061-0065
(2020/12/15)
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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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- 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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- 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; 0106-0111
(2020/09/16)
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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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- Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species
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Cyano-containing compounds constitute important pharmaceuticals, agrochemicals and organic materials. Traditional cyanation methods often rely on the use of toxic metal cyanides which have serious disposal, storage and transportation issues. Therefore, there is an increasing need to develop general and efficient catalytic methods for cyanide-free production of nitriles. Here we report the reductive cyanation of organic chlorides using CO2/NH3 as the electrophilic CN source. The use of tridentate phosphine ligand Triphos allows for the nickel-catalyzed cyanation of a broad array of aryl and aliphatic chlorides to produce the desired nitrile products in good yields, and with excellent functional group tolerance. Cheap and bench-stable urea was also shown as suitable CN source, suggesting promising application potential. Mechanistic studies imply that Triphos-Ni(I) species are responsible for the reductive C-C coupling approach involving isocyanate intermediates. This method expands the application potential of reductive cyanation in the synthesis of functionalized nitrile compounds under cyanide-free conditions, which is valuable for safe synthesis of (isotope-labeled) drugs.
- Dong, Yanan,Li, Yuehui,Yang, Peiju,Zhao, Shizhen
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- Nitrosation of Cyanamide: Preparation and Properties of the Elusive E- and Z-N'-Cyanodiazohydroxides
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Nitrosation of cyanamide leads to unstable E/Z-cyanodiazohydroxides that easily deprotonate to E/Z-cyanodiazotates. Pursuing observations of E. Drechsel 145 years ago, the structure and reactivity of those products was determined, mainly in aqueous solution. Depending on the pH, three different thermal decomposition pathways give either N2O + HCN or N2 + HNCO. They were evaluated experimentally and by quantum mechanical calculations.
- Guethner, Thomas,Huber, Evi,Sans, Juergen,Thalhammer, Franz
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supporting information
(2020/04/29)
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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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- Atomically Dispersed Ru on Manganese Oxide Catalyst Boosts Oxidative Cyanation
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There is a strong incentive for environmentally benign and sustainable production of organic nitriles to avoid the use of toxic cyanides. Here we report that manganese oxide nanorod-supported single-site Ru catalysts are active, selective, and stable for oxidative cyanation of various alcohols to give the corresponding nitriles with molecular oxygen and ammonia as the reactants. The very low amount of Ru (0.1 wt %) with atomic dispersion boosts the catalytic performance of manganese oxides. Experimental and theoretical results show how the Ru sites enhance the ammonia resistance of the catalyst, bolstering its performance in alcohol dehydrogenation and oxygen activation, the key steps in the oxidative cyanation. This investigation demonstrates the high efficiency of a single-site Ru catalyst for nitrile production.
- Gates, Bruce C.,Guan, Erjia,Meng, Xiangju,Wang, Chengtao,Wang, Hai,Wang, Liang,Wang, Sai,Xiao, Feng-Shou,Xu, Dongyang,Xu, Hua,Yang, Bo,Zhang, Jian
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p. 6299 - 6308
(2020/07/21)
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- Earth-Abundant Bimetallic Nanoparticle Catalysts for Aerobic Ammoxidation of Alcohols to Nitriles
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Heterogeneous nitrogen-doped carbon-incarcerated iron/copper bimetallic nanoparticle (NP) catalysts prepared from nitrogen-containing polymers were developed. These catalysts showed activity higher than that of the corresponding monometallic NPs for aerobic ammoxidation of alcohols to nitriles. The important procedure for high activity in the catalyst preparation was found to be a simultaneous reduction of two metal salts.
- Kobayashi, Shu,Yang, Xi,Yasukawa, Tomohiro
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p. 7543 - 7548
(2020/06/27)
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- Continuous-flow synthesis of nitriles from aldehydes via Schmidt reaction
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A continuous-flow synthesis of nitriles by Schmidt reaction has been developed. Using this procedure, a variety of aldehydes could be smoothly transformed into the desired nitriles in good to excellent yields. The mild reaction conditions and the flowing reaction system greatly improved the safety and make the reaction easy to scale up.
- Zhan, Wei,Tong, Meng,Ji, Ling,Zhang, Han,Ge, Zemei,Wang, Xin,Li, Runtao
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p. 973 - 976
(2019/01/29)
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- Visible light-induced direct conversion of aldehydes into nitriles in aqueous medium using Co@g-C3N4 as photocatalyst
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Unprecedented Co@g-C3N4 catalyzed visible light driven efficient conversion of a variety of aldehydes into corresponding nitriles is reported. Operational simplicity, excellent yield of pure products (87–94%), ambient reaction condition, using aqueous methanol as solvent, visible-light photocatalysis are the salient features of envisaged methodology for direct conversion of aldehydes into nitriles. Furthermore, reusability of Co@g-C3N4 was checked up to five runs and it was noticed that there was no substantial change in morphology as well as the catalytic efficiency of catalyst.
- Verma, Fooleswar,Shukla, Prashant,Bhardiya, Smita R.,Singh, Manorama,Rai, Ankita,Rai, Vijai K.
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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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p. 3190 - 3194
(2019/05/21)
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- Green synthesis of benzonitrile using ionic liquid with multiple roles as the recycling agent
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Preparation of benzonitrile from benzaldehyde and hydroxylamine hydrochloride is one of the most advantageous approaches. Nevertheless, it suffers from various constraints such as longer reaction time, corrosion and recovery of hydrochloric acid, the use of metal salt catalysts and their separation. For these reasons, a novel green benzonitrile synthetic route was proposed with ionic liquid as the recycling agent in this study. The results indicated that hydroxylamine 1-sulfobutyl pyridine hydrosulfate salt ((NH2OH)2·[HSO3-b-Py]·HSO4) was an expert alternative to hydroxylamine hydrochloride. Meanwhile, the ionic liquid [HSO3-b-Py]·HSO4 exhibited the multiple roles of co-solvent, catalysis and phase separation, thus the use of metal salt catalyst was eliminated, and no additional catalyst was needed. Hence, the separation process was greatly simplified. When the molar ratio of benzaldehyde to (NH2OH)2·[HSO3-b-Py]·HSO4 was 1:1.5, the volume ratio of paraxylene to [HSO3-b-Py]·HSO4 was 2:1, the benzaldehyde conversion and benzonitrile yield were both 100% at 120 °C in 2 h. Even better, the ionic liquid could be recovered easily by phase separation, and recycled directly after reaction. Additionally, this novel route is applicable to the green synthesis of a variety of aromatic, heteroaromatic and aliphatic nitriles with excellent yields.
- Li, Zhihui,Wang, Tingting,Qi, Xudong,Yang, Qiusheng,Gao, Liya,Zhang, Dongsheng,Zhao, Xinqiang,Wang, Yanji
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p. 17631 - 17638
(2019/06/24)
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- Thiocyanate radical mediated dehydration of aldoximes with visible light and air
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We developed a new means of activating aldoximes by an in situ generated thiocyanate radical from ammonium thiocyanate and molecular oxygen at room temperature. With a catalytic amount of organic dye aizenuranine as the photocatalyst, the dehydration of aldoximes proceeds smoothly under visible light irradiation, providing a simple to handle, excellent functional group tolerance, and metal-free protocol for a wide range of nitriles.
- Ban, Yong-Liang,Dai, Jian-Ling,Jin, Xiao-Ling,Zhang, Qing-Bao,Liu, Qiang
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supporting information
p. 9701 - 9704
(2019/08/15)
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- Solvent-Tailored Pd3P0.95 nano catalyst for amide-nitrile inter-conversion, the hydration of nitriles and transfer hydrogenation of the CO bond
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For the first time, a one pot thermolysis of [Pd(PPh3)2Cl2] prepared by reacting Ph3P with PdCl2 in a 2:1 molar ratio in MeOH at 280 °C in a trioctylphosphine (TOP) and oleylamine(OA)-octadecane(ODE) mixture (1:1) was used to prepare quantum dots (QDs; size ~2-3 nm) and nanoparticles (NPs; size ~13-14 nm), respectively, of composition Pd3P0.95. TEM, SEM-EDX, powder-XRD and XPS (for QDs only) were used to authenticate the two nanophases. 31P{1H}NMR experiments performed to monitor the progress of thermolysis reactions revealed that the phosphorus present in the Pd3P0.95 QDs had come from TOP, whereas in Pd3P0.95 NPs, its source is triphenylphosphine. The nature of the solvent did not affect the chemical composition of the nano-phase but controlled its size. Probably, solvent dependent, unique, single source precursors (SSPs) of palladium were generated in situ, and controlled the size. The catalytic activity of both Pd3P0.95 QDs and NPs was explored. The QDs were found to be efficient as a catalyst for the amide-nitrile interconversion at room temperature (yield up to 92% in 4 h), hydration of nitriles and transfer hydrogenation (TH) of carbonyl compounds with yields up to 96% in 3-4 h. The yields and reaction rates of amide-nitrile inter-conversion and TH when catalyzed by Pd3P0.95 QDs were found to be higher compared to the ones observed with the Pd/C catalyst. The binding energy of Pd(3d) in the X-ray photoelectron spectrum (XPS) of Pd3P0.95 indicated an electron transfer from the metal to phosphorus, resulting in electron deficient palladium, which facilitates the coordination of a substrate to Pd and drives the reaction. The reusability of Pd3P0.95 QDs for the interconversion was found to be up to 4-Times, while for the transfer hydrogenation of carbonyl compounds it was up to 6-Times, but with a diminished yield. Pd3P0.95 NPs were found to be less active (yield up to 36% in optimized reaction conditions) in comparison to Pd3P0.95 QDs. The mercury poisoning test suggested that the catalysis predominantly proceeded heterogeneously on the surface of the QDs. The PXRD and XPS results did not suggest a significant variation in the phase of QDs after the third catalytic cycle. The bleeding of Pd during catalysis (determined by flame AAS) and the agglomeration of QDs as supported by the SEM-EDX and TEM results are probably responsible for the reduction in the catalytic activity of QDs after reusing three times.
- Sharma, Alpesh K.,Joshi, Hemant,Bhaskar, Renu,Singh, Ajai K.
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supporting information
p. 10962 - 10970
(2019/07/31)
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- Ni-Catalyzed Reductive Cyanation of Aryl Halides and Phenol Derivatives via Transnitrilation
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Herein, we report a Ni-catalyzed reductive coupling for the synthesis of benzonitriles from aryl (pseudo)halides and an electrophilic cyanating reagent, 2-methyl-2-phenyl malononitrile (MPMN). MPMN is a bench-stable, carbon-bound electrophilic CN reagent that does not release cyanide under the reaction conditions. A variety of medicinally relevant benzonitriles can be made in good yields. Addition of NaBr to the reaction mixture allows for the use of more challenging aryl electrophiles such as aryl chlorides, tosylates, and triflates. Mechanistic investigations suggest that NaBr plays a role in facilitating oxidative addition with these substrates.
- Mills, L. Reginald,Graham, Joshua M.,Patel, Purvish,Rousseaux, Sophie A. L.
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p. 19257 - 19262
(2019/12/02)
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- Ni-Mediated Generation of "cN" Unit from Formamide and Its Catalysis in the Cyanation Reactions
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The in situ generation of a "cyano" unit from readily available organic precursors is of high interest in synthetic chemistry. Herein, we report the first example of Ni-mediated dehydration of formamide to form "CN" and its subsequent catalytic applications in the hydrocyanation of alkynes and cyanation of aryl halides. Formamide can serve as a convenient source for the nitrile unit, in that it releases water as the only byproduct.
- Yang, Luo,Liu, Yu-Ting,Park, Yoonsu,Park, Sung-Woo,Chang, Sukbok
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p. 3360 - 3365
(2019/03/26)
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- A carboxamide is the cyanogen source of aromatic nitrile to the preparation method of the (by machine translation)
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The invention discloses a method for preparing aromatic nitrile, is under the action of the nickel catalyst, in order to carboxamide is the cyanogen source, and with various substituents haloarene coupled reactions, preparing aromatic nitrile. The reaction temperature is 100 - 160 °C, the reaction time is 6 - 24 hours. It overcomes the traditional aromatic nitrile of the synthesis method operation of complex steps, requires the use of a toxic, more expensive, functionalization of the cyanogen source as the reaction raw material and the like. Compared with the traditional method, this method is simple to use cheap, green non-toxic of the formamide is cyano sources; without the need of external dehydrating agent, formamide in the nickel catalyst of the catalytic dehydration at the same time, with a nickel catalyst in coordination with the halogenated aromatic hydrocyanation, more economic, high-efficiency, environmental protection; at the same time the method exhibits good substrate universality, to air, moisture, light are not sensitive, high yield, product separation and purification is simple, with wide application. (by machine translation)
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Paragraph 0015; 0016; 0017; 0018-0024; 0116; 0117-0119
(2019/05/08)
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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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- 1,10-Phenanthroline- or Electron-Promoted Cyanation of Aryl Iodides
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A 1,10-phenanthroline-promoted cyanation of aryl iodides has been developed. 1,10-Phenanthroline worked as an organocatalyst for the reaction of aryl iodides with tetraalkylammonium cyanide to afford aryl cyanides. A similar reaction occurred through an electroreductive process.
- Hirata, Takayuki,Mandai, Hiroki,Midorikawa, Koji,Mitsudo, Koichi,Suga, Seiji,Yoshioka, Kazuki
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supporting information
p. 1209 - 1214
(2019/06/08)
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- Transformation of aromatic bromides into aromatic nitriles with n-BuLi, pivalonitrile, and iodine under metal cyanide-free conditions
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Various aromatic nitriles could be obtained in good yields by the treatment of aryl bromides with n-butyllithium and then pivalonitrile, followed by the treatment with molecular iodine at 70 °C, without metal cyanides under transition-metal-free conditions. The present reaction proceeds through the radical β-elimination of imino-nitrogen-centered radicals formed from the reactions of imines and N-iodoimines under warming conditions.
- Uchida, Ko,Togo, Hideo
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- Method for preparing nitrile
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The invention provides a method for preparing nitrile. Aldoxime carboxylic ester is used as a reactant to prepare a nitrile compound. The aldoxime carboxylic ester can be completely converted into corresponding nitrile under common catalysis of ferric salt and phenol within a few minutes. The method for preparing the nitrile has the advantages of gentle reaction conditions, simple and easy-to-getused reagents, cheap and environment-friendly catalyst, wide substrate application range, simple operation, rapid reaction and the like.
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Paragraph 0015
(2019/06/13)
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- Nickel-catalyzed cyanation of aryl halides and triflates using acetonitrile: Via C-CN bond cleavage assisted by 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine
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We developed a non-toxic cyanation reaction of various aryl halides and triflates in acetonitrile using a catalyst system of [Ni(MeCN)6](BF4)2, 1,10-phenanthroline, and 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine (Si-Me4-DHP). Si-Me4-DHP was found to function as a reductant for generating nickel(0) species and a silylation reagent to achieve the catalytic cyanation via C-CN bond cleavage.
- Ueda, Yohei,Tsujimoto, Nagataka,Yurino, Taiga,Tsurugi, Hayato,Mashima, Kazushi
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p. 994 - 999
(2019/02/03)
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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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- Preparation method for aromatic nitriles compound
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The invention discloses a preparation method for an aromatic nitriles compound. The preparation method comprises the following steps: using a methylbenzene derivative as shown in formula (I) as a rawmaterial, using nano ferrovanadium as a catalyst, and using hydrogen peroxide as a promoter, adding a ligand and an ammonia source, at a temperature of 80-180 DEG C, in an oxygen atmosphere, reactingfor 6-24 h in a condition that a working pressure is 0.1-1.5 MPa, to obtain a reaction mixture, after post-treatment, to obtain a target product of the aromatic nitriles compound as shown in a formula(II). The method is capable of realizing the conversion from methyl aromatics to the aromatic nitriles compound in a mild condition, and high in reaction yield, and has the industrialized applicationprospect. Oxygen is used as a cleaning oxidant, so the generation of poisonous and harmful by-products is reduced in a traditional inorganic salt oxidant reaction process. The preparation method is an environment-friendly strategy.
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Paragraph 0037; 0038; 0039
(2018/11/03)
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- Aerobic Oxidative Dehydrogenation of Amines Catalyzed by a Recoverable Ruthenium Catalyst under Mild Reaction Conditions
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A highly active catalyst based on perruthenate ions supported inside the channels of periodic mesoporous organosilica with a bridged imidazolium ionic liquid framework (Ru@PMO-IL) was developed. The material was found to be an efficient, durable, and recoverable catalyst for the oxidative dehydrogenation of various types of amines such as benzylic, aliphatic, and cyclic aliphatic amines under mild reaction conditions. The products were obtained in excellent yields with excellent selectivities.
- Karimi, Babak,Yari, Omolbanin,Khorasani, Mojtaba,Vali, Hojatollah,Mansouri, Fariborz
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p. 1783 - 1787
(2018/01/27)
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- Boosting Hydrogen Production by Anodic Oxidation of Primary Amines over a NiSe Nanorod Electrode
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For electrocatalytic water splitting, the sluggish anodic oxygen evolution reaction (OER) restricts the cathodic hydrogen evolution reaction (HER). Therefore, developing an alternative anodic reaction with accelerating kinetics to produce value-added chemicals, especially coupled with HER, is of great importance. Now, a thermodynamically more favorable primary amine (?CH2?NH2) electrooxidation catalyzed by NiSe nanorod arrays in water is reported to replace OER for enhancing HER. The increased H2 production can be obtained at cathode; meanwhile, a variety of aromatic and aliphatic primary amines are selectively electrooxidized to nitriles with good yields at the anode. Mechanistic investigations suggest that NiII/NiIII may serve as the redox active species for the primary amines transformation. Hydrophobic nitrile products can readily escape from aqueous electrolyte/electrode interface, avoiding the deactivation of the catalyst and thus contributing to continuous gram-scale synthesis.
- Chong, Xiaodan,Huang, Yi,Liang, Yu,Liu, Cuibo,Zhang, Bin
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supporting information
p. 13163 - 13166
(2018/09/21)
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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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- Pd-Catalyzed Cyanation of (Hetero)Aryl Halides by Using Biphosphine Ligands
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Tetraadamantylbiphosphine (TABP; L1), which showed superior activity in the palladium-catalyzed cyanation of 4-chloroanisole compared to standard phosphines, was synthesized as a new ligand. The generality of the new catalytic system was shown by the cyanation reaction of approximately 30 (hetero)aryl halides including hindered, electron-rich, and electron-poor aryl chlorides. These reactions constitute the first examples of using biphosphine ligands in Pd-catalyzed coupling reactions.
- Zhang, Shaoke,Neumann, Helfried,Beller, Matthias
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supporting information
p. 67 - 70
(2017/11/27)
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