- Photochemical Reactions in Polyethylene Glycol. 2. Photo-induced Nucleophilic Substitution of Dimethoxybenzenes in the Presence of Polyethylene Glycol
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Polyethylene glycol can replace crown ether as co-solvent for photochemical substitution reactions of dimethoxybenzenes with KCN in CH2Cl2 in either the presence or the absence of terephthalonitrile.
- Suzuki, Nobutaka,Ayaguchi, Yasuo,Izawa, Yasuji
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Read Online
- Anomaluos Effects during Aromatic Nucleophilic Photosubstitutions of 2- and 4-Fluoroanisoles in Solvent Mixtures of Water and tert-Butyl Alcohol
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The rate constant ratio for removal of fluorine by either cyano or hydroxy during aromatic nucleophilic photosubstitutions on 2- or 4-fluoroanisole displays a remarkable dependence upon the composition of the water/tert-butyl alcohol solvent and the distance between the methoxy group and the site of substitution in the solutes.
- Liu, Jerry H.,Weiss, Richard G.
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- Nickel/zinc-mediated synthesis of aromatic nitriles from aromatic oxime ethers
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Treatment of o-alkoxybenzaldoxime ethers 3 with an equimolar amount of NiCl2 and 3 equimolar amounts of Zn gave o-alkoxybenzonitriles 4 in good yields. It is suggested that the reaction proceed via coordination of the ether oxygen atom of alkyl
- Maeyama, Katsuya,Kobayashi, Masato,Kato, Hiroshi,Yonezawa, Noriyuki
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Read Online
- Palladium-catalyzed cyanation of hindered, electron-rich aryl triflates by zinc cyanide
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We examined the palladium-catalyzed cyanation of hindered, electron- rich aryl triflates by zinc cyanide using 2-methoxyphenyl trifluoromethanesulfonate (4 as a model compound. The reaction with two equivalents of Zn(CN)2 and catalytic Pd(PPh3)4 in DMF at 120°C for 2 hr afforded 2-methoxybenzonitrile (5) in 81% yield. The synthesis of 3-cyano-3- desoxynaltrexone (3), which had not previouly been obtained by the reaction with potassium or sodium cyanide as a cyanide source, was achieved by applying this procedure to its corresponding triflate 2.
- Kubota, Hitoshi,Rice, Kenner C.
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Read Online
- 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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- Cu-Catalyzed Phenol O-Methylation with Methylboronic Acid
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A Cu-catalyzed oxidative cross-coupling of phenols with methylboronic acid to form aryl methyl ethers has been developed, expanding the scope of Chan-Evans-Lam alkylation. Electron-deficient phenol derivatives with a broad array of functional groups are methylated in high yields. Increased reaction temperature and catalyst loading enables the methylation of substrates incorporating pyridine and dihydroquinolone motifs. Electron-rich phenol derivatives are poor substrates for the methylation; the characterization of C?H homodimerization products formed from these substrates illuminates a competing mechanistic pathway.
- Bartlett, Mairead E.,Chavez, Angela K.,Gaffney, Uma Bhagwat,Gorin, David J.,Lee, Joyce,Sharew, Betemariam,Wu, Miranda,Zhu, Yingchuan
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supporting information
p. 5661 - 5664
(2021/11/11)
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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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- Nickel-Catalyzed Cyanation of Aryl Thioethers
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A nickel-catalyzed cyanation of aryl thioethers using Zn(CN)2 as a cyanide source has been developed to access functionalized aryl nitriles. The ligand dcype (1,2-bis(dicyclohexylphosphino)ethane) in combination with the base KOAc (potassium acetate) is essential for achieving this transformation efficiently. This reaction involves both a C-S bond activation and a C-C bond formation. The scalability, low catalyst and reagents loadings, and high functional group tolerance have enabled both late-stage derivatization and polymer recycling, demonstrating the reaction's utility across organic chemistry.
- Delcaillau, Tristan,Woenckhaus-Alvarez, Adrian,Morandi, Bill
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supporting information
p. 7018 - 7022
(2021/09/13)
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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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- 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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- Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
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We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
- Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
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supporting information
p. 3723 - 3728
(2021/04/07)
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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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- Visible-Light-Promoted Metal-Free Synthesis of (Hetero)Aromatic Nitriles from C(sp3)?H Bonds**
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The metal-free activation of C(sp3)?H bonds to value-added products is of paramount importance in organic synthesis. We report the use of the commercially available organic dye 2,4,6-triphenylpyrylium tetrafluoroborate (TPP) for the conversion of methylarenes to the corresponding aryl nitriles via a photocatalytic process. Applying this methodology, a variety of cyanobenzenes have been synthesized in good to excellent yield under metal- and cyanide-free conditions. We demonstrate the scope of the method with over 50 examples including late-stage functionalization of drug molecules (celecoxib) and complex structures such as l-menthol, amino acids, and cholesterol derivatives. Furthermore, the presented synthetic protocol is applicable for gram-scale reactions. In addition to methylarenes, selected examples for the cyanation of aldehydes, alcohols and oximes are demonstrated as well. Detailed mechanistic investigations have been carried out using time-resolved luminescence quenching studies, control experiments, and NMR spectroscopy as well as kinetic studies, all supporting the proposed catalytic cycle.
- Murugesan, Kathiravan,Donabauer, Karsten,K?nig, Burkhard
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supporting information
p. 2439 - 2445
(2020/12/07)
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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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- A Molecular Iron-Based System for Divergent Bond Activation: Controlling the Reactivity of Aldehydes
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The direct synthesis of amides and nitriles from readily available aldehyde precursors provides access to functional groups of major synthetic utility. To date, most reliable catalytic methods have typically been optimized to supply one product exclusively. Herein, we describe an approach centered on an operationally simple iron-based system that, depending on the reaction conditions, selectively addresses either the C=O or C-H bond of aldehydes. This way, two divergent reaction pathways can be opened to furnish both products in high yields and selectivities under mild reaction conditions. The catalyst system takes advantage of iron's dual reactivity capable of acting as (1) a Lewis acid and (2) a nitrene transfer platform to govern the aldehyde building block. The present transformation offers a rare control over the selectivity on the basis of the iron system's ionic nature. This approach expands the repertoire of protocols for amide and nitrile synthesis and shows that fine adjustments of the catalyst system's molecular environment can supply control over bond activation processes, thus providing easy access to various products from primary building blocks.
- Chatterjee, Basujit,Jena, Soumyashree,Chugh, Vishal,Weyhermüller, Thomas,Werlé, Christophe
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p. 7176 - 7185
(2021/06/30)
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- Highly Efficient Oxidative Cyanation of Aldehydes to Nitriles over Se,S,N-tri-Doped Hierarchically Porous Carbon Nanosheets
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Oxidative cyanation of aldehydes provides a promising strategy for the cyanide-free synthesis of organic nitriles. Design of robust and cost-effective catalysts is the key for this route. Herein, we designed a series of Se,S,N-tri-doped carbon nanosheets with a hierarchical porous structure (denoted as Se,S,N-CNs-x, x represents the pyrolysis temperature). It was found that the obtained Se,S,N-CNs-1000 was very selective and efficient for oxidative cyanation of various aldehydes including those containing other oxidizable groups into the corresponding nitriles using ammonia as the nitrogen resource below 100 °C. Detailed investigations revealed that the excellent performance of Se,S,N-CNs-1000 originated mainly from the graphitic-N species with lower electron density and synergistic effect between the Se, S, N, and C in the catalyst. Besides, the hierarchically porous structure could also promote the reaction. Notably, the unique feature of this metal-free catalyst is that it tolerated other oxidizable groups, and showed no activity on further reaction of the products, thereby resulting in high selectivity. As far as we know, this is the first work for the synthesis of nitriles via oxidative cyanation of aldehydes over heterogeneous metal-free catalysts.
- Hua, Manli,Song, Jinliang,Huang, Xin,Liu, Huizhen,Fan, Honglei,Wang, Weitao,He, Zhenhong,Liu, Zhaotie,Han, Buxing
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supporting information
p. 21479 - 21485
(2021/08/23)
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- Copper-Catalyzed One-Pot Synthesis of Quinazolinones from 2-Nitrobenzaldehydes with Aldehydes: Application toward the Synthesis of Natural Products
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A novel, efficient, and atom-economical approach for the construction of quinazolinones from 2-nitrobenzaldehydes has been unveiled via copper-catalyzed nitrile formation, hydrolysis, and reduction in one pot for the first time. In this reaction, urea is used as a source of nitrogen for nitrile formation, hydrazine hydrate is used for both the reduction of the nitro group and the hydrolysis of nitrile, and atmospheric oxygen is used as the sole oxidant. The method portrays a wide substrate scope with good functional group tolerances. Moreover, this method was applied for the synthesis of schizocommunin, tryptanthrin, phaitanthrin-A, phaitanthrin-B, and 8H-quinazolino[4,3-b]quinazolin-8-one.
- Pal, Shantanu,Sahoo, Subrata
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p. 18067 - 18080
(2021/12/06)
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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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- 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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p. 3583 - 3588
(2020/08/05)
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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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- 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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- Metal-free dehydrosulfurization of thioamides to nitriles under visible light
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A visible light-mediated, metal-free dehydrosulfurization reaction of thioamides to nitriles is described. This reaction features high yields, mild reaction conditions, and the use of a cheap organic dye as the photoredox catalyst and air as the oxidant.
- Xu, Tianxiao,Cao, Tianpeng,Feng, Qingyuan,Huang, Shenlin,Liao, Saihu
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supporting information
p. 5151 - 5153
(2020/05/26)
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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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- 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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- Acetic Anhydride-Acetic Acid as a New Dehydrating Agent of Aldoximes for the Preparation of Nitriles: Preparation of 2-Cyanoglycals
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Glycals, 1,2-unsatrated carbohydrates, are versatile building blocks for the synthesis of various scaffolds. Despite their potential to serve as suitable precursors in diversity-oriented synthesis, 2-cyanoglycals are less explored in terms of their synthesis and derivatization. Herein, we report a combination of Ac 2 O and AcOH as new and efficient dehydrating agent of aldoximes for the synthesis of 2-cyanoglycals. In comparison to the conventional dehydrating system of Ac 2 O-base (such as NaOH, NaOAc and K 2 CO 3), the current protocol provides superior yields and faster reaction rates. The scope and limitations of the dehydrating system are investigated.
- Kinfe, Henok H.,Mabasa, Jackie,Mabasa, Tommy F.,Makhubela, Banothile C. E.,Simelane, Mthokozisi,Vatsha, Banele
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supporting information
p. 991 - 996
(2020/06/10)
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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; 0148-0153
(2020/09/16)
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- Silicon hydrogenation reaction method of organic boron and inorganic alkali catalysis amide (by machine translation)
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The method is characterized in that organic boron and inorganic bases are used as catalysts, silane is used as a reducing agent, primary amide is reduced to primary amine or dehydration dinitrile, the secondary amide is reduced to a secondary amine or aldimine, and the tertiary amide is reduced to tertiary amine. The method has the advantages of simple operation, mild reaction conditions, wide substrate universality, good functional group compatibility and the like, and has the characteristics of good stability, cheap and accessible catalyst, simple and convenient operation, high practicality and the like. (by machine translation)
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Paragraph 0201-0207; 0233-0236
(2020/08/18)
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- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
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We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
- Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
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p. 378 - 385
(2020/10/02)
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- Method for 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 0040; 0041
(2020/09/12)
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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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- Synthesis process of 2-amino-3,5-dinitrobenzonitrile
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The invention provides a synthesis process of 2-amino-3,5-dinitrobenzonitrile. The process comprises the following steps that S1, chlorobenzonitrile and sodium methoxide are dissolved in a specific solvent, a reaction is carried out in an autoclave, after the reaction is completed, the temperature is reduced to the room temperature, an acid is used for neutralizing the mixture to be neutral, and asolvent and a first intermediate 2-methoxybenzonitrile are separated from a reaction filter liquor through rectification; S2, the first intermediate 2-methoxybenzonitrile is dissolved in the solventfor a nitration reaction, the reaction endpoint is monitored through HPLC, after the reaction is completed, elutriation operation is carried out, filtration is carried out to obtain a second intermediate 2-methoxy-3,5-dinitrobenzonitrile, and a solvent and remaining 2-methoxy-3,5-dinitrobenzonitrile are separated from the filter liquor through steam distillation; S3, the second intermediate 2-methoxy-3,5-dinitrobenzonitrile is dispersed in an ammoniation solvent, the mixture is transferred into the autoclave, a certain amount of liquid ammonia is introduced for an ammoniation reaction, and after the reaction is completed, filtration is carried out to obtain the product 2-amino-3,5-dinitrobenzonitrile.
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Paragraph 0031-0032; 0036-0037; 0040-0041; 0044-0045
(2019/10/15)
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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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- 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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- Cyanation of Anilines to Aryl Nitriles Using tert-Butyl Isocyanide: A Simple and Copper-free Procedure
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In this manuscript, a simple and copper-free procedure for the synthesis of aryl nitrile derivatives from anilines is described. Under the improved protocol, the anilines were reacted with tert-butyl isocyanide under a mild reaction condition without the use of solvents and copper catalyst to synthesize benzonitriles. This copper-free Sandmeyer-type reaction could tolerate a range of anilines bearing different functional groups and also can be conducted even without the exclusion of air. In addition, this method has afforded the aryl nitriles in moderate to good yields (52–81%). The obtained results in this study reveal that the tert-butyl isocyanide as a potential cyanide source for the cyanation reaction.
- Chia, Poh Wai,Yong, Fu Siong Julius,Mohamad, Habsah,Kan, Su-Yin
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supporting information
p. 939 - 942
(2019/08/21)
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- Iron and Phenol Co-Catalysis for Rapid Synthesis of Nitriles under Mild Conditions
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A mild, scalable, high yielding, and rapid route to access diverse nitriles from aldehyde oxime esters enabled by iron(III) and phenol co-catalysis has been developed. The reaction was performed at room temperature to give nitriles in excellent yield within minutes. Mechanistic studies show that the reaction may proceed through a radical process in which benzoyl aldehyde oxime is not only a substrate, but also an ancillary ligand to support iron salt in the promotion of the transformation.
- Meng, Hong,Gao, Sen,Luo, Meiming,Zeng, Xiaoming
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p. 4617 - 4623
(2019/07/15)
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- Dual Ligand-Enabled Nondirected C-H Cyanation of Arenes
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Aromatic nitriles are key structural units in organic chemistry and, therefore, highly attractive targets for C-H activation. Herein, the development of an arene-limited, nondirected C-H cyanation based on the use of two cooperatively acting commercially available ligands is reported. The reaction enables the cyanation of arenes by C-H activation in the absence of directing groups and is therefore complementary to established approaches.
- Chen, Hao,Mondal, Arup,Wedi, Philipp,Van Gemmeren, Manuel
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p. 1979 - 1984
(2019/02/19)
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- Palladium-Catalyzed Late-Stage Direct Arene Cyanation
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Methods for direct benzonitrile synthesis are sparse, despite the versatility of cyano groups in organic synthesis and the importance of benzonitriles for the dye, agrochemical, and pharmaceutical industries. We report the first general late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance. The reaction is enabled by a dual-ligand combination of quinoxaline and an amino acid-derived ligand. The method is applicable to direct cyanation of several marketed small-molecule drugs, common pharmacophores, and organic dyes. Benzonitriles are some of the most versatile building blocks for organic synthesis, in particular in the pharmaceutical industry, but general methods to make them by direct C–H functionalization are unknown. In this issue of Chem, Ritter and coworkers describe a late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance, enabled by a palladium-dual-ligand catalyst system. The reaction may serve for the late-stage modification of drug candidates. Aryl nitriles constitute an important class of organic compounds that are widely found in natural products, pharmaceuticals, agricultural chemicals, dyes, and materials. Moreover, nitriles are versatile building blocks to access numerous other important molecular structure groups. However, no general method for direct aromatic C–H cyanation is known. All approaches to date require either an appropriate directing group or reactive electron-rich substrates, such as indoles, which limit their synthetic applications. Here we describe an undirected, palladium-catalyzed late-stage aryl C–H cyanation reaction for the synthesis of complex aryl nitriles that would otherwise be more challenging to produce. The wide substrate scope and good functional-group tolerance of this reaction provide direct and quick access to structural diversity for pharmaceutical and agrochemical development.
- Zhao, Da,Xu, Peng,Ritter, Tobias
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supporting information
p. 97 - 107
(2019/01/21)
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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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- Efficient cyanation of aryl halides with K4[Fe(CN)6] catalyzed by encapsulated palladium nanoparticles in biguanidine–chitosan matrix as core–shell recyclable heterogeneous nanocatalyst
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Palladium nanoparticles encapsulated in biguanidine–functionalized chitosan matrix (Pd@CS–biguanidine) was applied as a reusable and core–shell nanocatalyst for cyanation of aryl iodides and bromides with K4[Fe(CN)6] as the cyanating agent. The nitriles were generated in good to excellent yield and the catalyst can be recycled and reapplied up to seven times with no significant change in its catalytic performance.
- Veisi, Hojat
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p. 212 - 216
(2019/01/03)
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- Application of biosynthesized palladium nanoparticles (Pd NPs) on Rosa canina fruit extract-modified graphene oxide as heterogeneous nanocatalyst for cyanation of aryl halides
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A green palladium (Pd)-based catalyst supported on Rosa canina fruit extract-modified graphene oxide [Pd nanoparticles (NPs)/reduced graphene oxide (RGO)-Rosa canina] hybrid materials has been used as a recoverable and heterogeneous nanocatalyst for cyanating aryl halides using K4[Fe (CN)6] as the resource of cyanide. The nitriles were achieved in good to high yield, and the catalyst can be recovered and reused for up to seven cycles with no remarkable decrease in its catalytic activity.
- Hemmati, Saba,Sedrpoushan, Alireza,Soudalizadeh, Nazanin,Khosravi, Kaveh,Hekmati, Malak
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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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- 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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- SO 2 F 2 -Promoted Dehydration of Aldoximes: A Rapid and Simple Access to Nitriles
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A rapid, simple and mild process for the dehydration of aldoximes to give the corresponding nitriles, which utilizes SO 2 F 2 as an efficient reagent, has been developed. A variety of (hetero)arene, alkene, alkyne and aliphatic aldoximes proceeded with high efficiency to afford nitriles in excellent to quantitative yields with great functional group compatibilities in acetonitrile under ambient conditions. Furthermore, an eco-friendly synthetic protocol to access nitriles from aldehydes with ortho -, meta - and para -nitrile groups was also described in aqueous methanol by using inorganic base Na 2 CO 3, and a one-pot synthetic strategy to generate nitriles from aldehydes was proved to be feasible.
- Ding, Chengrong,Mei, Guangyao,Wang, Haibo,Zhang, Guofu,Zhao, Yiyong
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supporting information
p. 1484 - 1488
(2019/07/15)
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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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- 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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- 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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- 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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- A BEt3-Base catalyst for amide reduction with silane
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Reported herein is the development of a simple but practical catalytic system for the selective reduction of amides with hydrosilane or hydrosiloxane. Low-cost and readily available triethylborane (1.0 M in THF), in combination with a catalytic amount of an alkali metal base, was found to catalyze the reduction of all three amide classes (tertiary, secondary, and primary amides) to form amines under mild conditions. In addition, the selective transformation of secondary amides to aldimines and primary amides to nitriles can also be achieved by using a proper combination of BEt3 and base. The scope of these BEt3-base-catalyzed amide hydrosilylation reactions has been explored in depth. Preliminary results of mechanistic studies suggest a modified Piers' silane Si-H···B activation mode wherein the hydride abstraction by BEt3 is promoted by the coordination of an alkoxide or hydroxide anion to the Si center.
- Yao, Wubing,Fang, Huaquan,He, Qiaoxing,Peng, Dongjie,Liu, Guixia,Huang, Zheng
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- A BEt3-Base Catalyst for Amide Reduction with Silane
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Reported herein is the development of a simple but practical catalytic system for the selective reduction of amides with hydrosilane or hydrosiloxane. Low-cost and readily available triethylborane (1.0 M in THF), in combination with a catalytic amount of an alkali metal base, was found to catalyze the reduction of all three amide classes (tertiary, secondary, and primary amides) to form amines under mild conditions. In addition, the selective transformation of secondary amides to aldimines and primary amides to nitriles can also be achieved by using a proper combination of BEt3 and base. The scope of these BEt3-base-catalyzed amide hydrosilylation reactions has been explored in depth. Preliminary results of mechanistic studies suggest a modified Piers' silane Si-H···B activation mode wherein the hydride abstraction by BEt3 is promoted by the coordination of an alkoxide or hydroxide anion to the Si center.
- Yao, Wubing,Fang, Huaquan,He, Qiaoxing,Peng, Dongjie,Liu, Guixia,Huang, Zheng
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p. 6084 - 6093
(2019/05/24)
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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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