- Lewis Acid-Mediated Cyanation of Phenols Using N-Cyano-N-phenyl-p-toluenesulfonamide
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Lewis acid-mediated cyanation of phenol derivatives with N-cyano-N-phenyl-p-toluenesulfonamide (NCTS) has been developed. The reaction proceeded efficiently with high regioselectivity to produce aromatic nitriles in moderate to excellent yields, which provides a direct and practical access to valuable products. (Figure presented.).
- Zhang, Wu,Li, Tao,Wang, Qingli,Zhao, Wanxiang
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supporting information
p. 4914 - 4918
(2019/11/03)
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- Highly Efficient Microwave-assisted One-Pot Synthesis of Aromatic Nitriles from Aromatic Aldehydes
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A highly efficient and environmentally benign protocol is described for the microwave-assisted one-pot synthesis of aromatic nitriles from aromatic aldehydes by the reaction with hydroxylamine hydrochloride in DMSO, which involves the intermediate formation of aldoximes and subsequent dehydration. The developed synthetic methodology can be readily accomplished with various aldehydes containing both electron-donor and electron-acceptor groups, providing excellent yields of the target products in shorter reaction times (1–2 min) compared to previously reported methodologies.
- Pujari,Thorat,Mahipal,Bhondwe
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p. 702 - 706
(2019/07/17)
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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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- Direct C-H Cyanation of Arenes via Organic Photoredox Catalysis
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Methods for the direct C-H functionalization of aromatic compounds are in demand for a variety of applications, including the synthesis of agrochemicals, pharmaceuticals, and materials. Herein, we disclose the construction of aromatic nitriles via direct C-H functionalization using an acridinium photoredox catalyst and trimethylsilyl cyanide under an aerobic atmosphere. The reaction proceeds at room temperature under mild conditions and has proven to be compatible with a variety of electron-donating and -withdrawing groups, halogens, and nitrogen- and oxygen-containing heterocycles, as well as aromatic-containing pharmaceutical agents.
- McManus, Joshua B.,Nicewicz, David A.
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supporting information
p. 2880 - 2883
(2017/03/11)
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- Electroorganic synthesis of nitriles via a halogen-free domino oxidation-reduction sequence
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A direct electroorganic sequence yielding nitriles from oximes in undivided cells is reported. Despite the fact that intermediate nitrile oxides might be formed, the method is viable to prepare benzonitriles without substituents ortho to the aldoxime moiety. This constant current method is easy to perform for a broad scope of substrates and employs common electrodes, such as graphite and lead.
- Hartmer, Marius F.,Waldvogel, Siegfried R.
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supporting information
p. 16346 - 16348
(2015/11/16)
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- Facile one-pot transformation of arenes into aromatic nitriles under metal-cyanide-free conditions
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Electron-rich arenes bearing methyl or methoxy groups on the aromatic ring were treated with dichloromethyl methyl ether and ZnBr2, and then with molecular iodine and aq. ammonia to give the corresponding aromatic nitriles in good yields. Using this method, febuxostat was efficiently prepared from 4-bromophenol in four steps. The method can be used for the preparation of aromatic nitriles from arenes in one pot under metal-cyanide-free conditions. Various electron-rich arenes could be effectively converted into the corresponding aromatic nitriles in good yields, by treatment with ZnBr2 and dichloromethyl methyl ether, followed by reaction with molecular iodine and aq. ammonia.
- Tamura, Toshiyuki,Moriyama, Katsuhiko,Togo, Hideo
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p. 2023 - 2029
(2015/03/18)
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- Pd(OAc)2/DPPF-catalysed microwave-assisted cyanide-free synthesis of aryl nitriles
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This study reports microwave-assisted cyanide-free synthesis of aryl nitriles from aryl halides using palladium acetate/1,1-bis(diphenylphosphino) ferrocene as a new catalyst system. Reported protocol is a rapid, cyanide-free, single step reaction, wherein formamide acts as a solvent as well as a source of cyanide. The use of microwave increases the rate of reaction substantially and it was observed that aryl nitriles can be synthesised in 50 min of microwave irradiation compared to conventional thermal heating protocol which requires 48 h.
- Sawant, Dinesh N.,Bhanage, Bhalchandra M.
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p. 319 - 324
(2014/06/09)
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- Practical synthesis of aromatic nitriles via gallium-catalysed electrophilic cyanation of aromatic C-H bonds
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A gallium-catalysed, direct cyanation reaction of aromatic and heteroaromatic C-H bonds with cyanogen bromide was developed as a practical synthetic method for the preparation of aromatic nitriles. The Royal Society of Chemistry 2012.
- Okamoto, Kazuhiro,Watanabe, Masahito,Murai, Masahito,Hatano, Ryo,Ohe, Kouichi
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supporting information; experimental part
p. 3127 - 3129
(2012/04/23)
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- Practical one-pot transformation of electron-rich aromatics into aromatic nitriles with molecular iodine and aq NH3 using Vilsmeier-Haack reaction
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Various electron-rich aromatics could be efficiently transformed into the corresponding aromatic nitriles in good to moderate yields by treatment with DMF and POCl3, followed by the reaction with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH) in aq NH3. Some of less reactive aromatics, such as anisole, 1,2-dimethoxybenzene, 1,4-dimethoxybenzene, and mesityrene, could be also transformed into the corresponding aromatic nitriles in good to moderate yields using N-methylformanilide and O(POCl 2)2, followed by the reaction with molecular iodine in aq NH3. Moreover, propiophenone derivatives could be successfully transformed into the corresponding β-chlorocinnamonitriles by the reaction with DMF and POCl3, followed by the reaction with molecular iodine and aq NH3. These reactions are novel metal-free one-pot methods for the preparation of aromatic nitriles from electron-rich aromatics and β-chlorocinnamonitriles from propiophenones.
- Ushijima, Sousuke,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 4588 - 4595
(2012/07/27)
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- Cyanides-free cyanation of aryl halides using formamide
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A novel method for cyanation of aryl halides using formamide as a non-toxic cyanide source is reported. It is a single-step, solvent-free method wherein formamide itself acts as solvent as well as source of cyanide in the presence of phosphorus oxychloride and palladium acetate/xantphos catalyst. Aryl iodides as well as aryl bromides provided moderate to excellent yields of up to 93%. Copyright
- Sawant, Dinesh N.,Wagh, Yogesh S.,Tambade, Pawan J.,Bhatte, Kushal D.,Bhanage, Bhalchandra M.
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experimental part
p. 781 - 787
(2011/06/11)
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- Straightforward conversion of arene carboxylic acids into aryl nitriles by palladium-catalyzed decarboxylative cyanation reaction
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A one-pot procedure to convert aromatic carboxylic acids into aromatic nitriles is described. The methodology is based on a palladium(II)-catalyzed decarboxylative cyanation reaction using cyanohydrins as soluble cyanide sources. The described reaction worked on a panel of substrates and is additionally of particular interest for the straightforward preparation of 13C- or 14C-labeled compounds.
- Ouchaou, Kahina,Georgin, Dominique,Taran, Frédéric
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experimental part
p. 2083 - 2086
(2010/10/03)
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- Metal-free one-pot conversion of electron-rich aromatics into aromatic nitriles
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Various electron-rich aromatics could be smoothly converted into the corresponding aromatic nitriles in good to moderate yields by treatment of electron-rich aromatics with POCl3 and DMF, followed by treatment with molecular iodine in aqueous ammonia. The present reaction is a novel metal-free one-pot method for the preparation of aromatic nitriles from electron-rich aromatics.
- Ushijima, Sousuke,Togo, Hideo
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experimental part
p. 1067 - 1070
(2010/06/14)
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- A clean conversion of aldehydes to nitriles using a solid-supported hydrazine
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A polymer-supported hydrazine reagent has been applied to the conversion of a range of aldehydes to nitriles, providing a clean and efficient route to more diverse building blocks for combinatorial chemistry programmes.
- Baxendale, Ian R.,Ley, Steven V.,Sneddon, Helen F.
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p. 775 - 777
(2007/10/03)
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- Photochemical Reactions of Aromatic Compounds. Part 34. Direct Photocyanation of Arenes with Sodium Cyanide in the Presence of Electron Acceptors
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Efficient photocyanation of various arenes with sodium cyanide in 9:1 acetonitrile-water occurs in the presence of such electron acceptors as p-dicyanobenzene, 1-cyanonaphthalene, or 9-cyanophenanthrene.Under nitrogen, photocyanation of phenanthrene, anthracene, naphthalene, and 2,3-dimethylnaphthalene gives both the corresponding hydrocyanation products and the aromatic nitriles, while complex mixtures are formed with other arenes.Under oxygen, a variety of arenes which are electron donors in nature can be efficiently cyanated upon irradiation to give the aromatic nitriles.Cyanation of naphthalene derivatives gives only 1-cyanonaphthalene compounds whereas phenanthrene and anthracene are cyanated at C-9.
- Yasuda, Masahide,Pac, Chyondgjin,Sakurai, Hiroshi
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p. 746 - 750
(2007/10/02)
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