- Decarbonylative Synthesis of Aryl Nitriles from Aromatic Esters and Organocyanides by a Nickel Catalyst
-
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
-
supporting information
p. 1555 - 1559
(2020/11/10)
-
- Nickel-Catalyzed Transformation of Alkene-Tethered Oxime Ethers to Nitriles by a Traceless Directing Group Strategy
-
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
-
p. 2654 - 2665
(2020/02/04)
-
- Organophotochemical SNAr Reactions of Mildly Electron-Poor Fluoroarenes
-
C–F functionalization of arenes with a range of alcohol and pyrazole nucleophiles has been achieved without the need for metal catalysts or highly electron-poor substrates. Treatment of fluoroarenes with alcohols or pyrazoles and DDQ under irradiation by blue LED light provides the corresponding substituted products. The procedure is complementary to classical SNAr chemistry which generally requires basic reaction conditions and high temperatures, and provides products under non-basic conditions at ≈ 40 °C.
- Burton, Jonathan W.,Genovino, Julien,Lian, Yajing,Monck, Nat,Sheridan, Thomas,Yayla, Hatice G.
-
supporting information
p. 2766 - 2770
(2020/05/18)
-
- 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
-
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
-
p. 994 - 999
(2019/02/03)
-
- Pd Catalysis in Cyanide-Free Synthesis of Nitriles from Haloarenes via Isoxazolines
-
A method to obtain aryl nitriles from the corresponding halides by Pd catalysis, in the absence of any cyanide source, is reported. The reaction of an aryl halide, ethyl nitroacetate, and an olefin readily delivers an aromatic nitrile. A variety of aryl iodides/bromides have been converted into the corresponding cyanoarenes in fair to excellent yields. The reaction likely involves the following steps: (a) Pd-catalyzed α-arylation of ethyl nitroacetate; (b) nitrile oxide formation; (c) [3 + 2]-cycloaddition with an olefin to provide an isoxazoline; (d) isoxazoline cleavage to benzonitrile formation.
- Maestri, Giovanni,Ca?eque, Tatiana,Della Ca, Nicola,Derat, Etienne,Catellani, Marta,Chiusoli, Gian Paolo,Malacria, Max
-
supporting information
p. 6108 - 6111
(2016/12/09)
-
- Cyanation of Phenol Derivatives with Aminoacetonitriles by Nickel Catalysis
-
Generation of useful arylnitrile structures from simple aromatic feedstock chemicals represents a fundamentally important reaction in chemical synthesis. The first nickel-catalyzed cyanation of phenol derivatives with metal-free cyanating agents, aminoacetonitriles, is described. A nickel-based catalytic system consisting of a unique diphosphine ligand such as dcype or dcypt enables the cyanation of versatile phenol derivatives such as aryl carbamates and aryl pivalates. The use of aminoacetonitriles as a cyanating agent leads to an environmentally and easy-to-use method for arylnitrile synthesis.
- Takise, Ryosuke,Itami, Kenichiro,Yamaguchi, Junichiro
-
supporting information
p. 4428 - 4431
(2016/10/12)
-
- Facile one-pot transformation of arenes into aromatic nitriles under metal-cyanide-free conditions
-
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
-
p. 2023 - 2029
(2015/03/18)
-
- Nitrogen dioxide-catalyzed electrophilic iodination of arenes
-
Nitrogen dioxide is demonstrated to be an effective catalyst precursor for the iodination of alkoxy-substituted benzenes and naphthalenes. Different from the transition metal catalysts, nitrogen dioxide can be easily separated from the final products, and is free of heavy metal waste. Although the present catalyst precursor is toxic, it does not stain the final products due to its low-boiling character. No other reagents apart from 0.5 equiv. of iodine (I 2), 6.5 mol% nitrogen dioxide and acetonitrile solvent were used in the iodination, and basically all the iodine atoms in the iodine source were transferred to the iodination products, showing that the presented protocol is highly atom-economic and practical. Copyright
- Ren, Yun-Lai,Shang, Huantao,Wang, Jianji,Tian, Xinzhe,Zhao, Shuang,Wang, Qian,Li, Fuwei
-
supporting information
p. 3437 - 3442
(2013/12/04)
-
- Practical one-pot transformation of electron-rich aromatics into aromatic nitriles with molecular iodine and aq NH3 using Vilsmeier-Haack reaction
-
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
-
experimental part
p. 4588 - 4595
(2012/07/27)
-
- Practical synthesis of aromatic nitriles via gallium-catalysed electrophilic cyanation of aromatic C-H bonds
-
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
-
supporting information; experimental part
p. 3127 - 3129
(2012/04/23)
-
- Metal-free one-pot conversion of electron-rich aromatics into aromatic nitriles
-
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
-
experimental part
p. 1067 - 1070
(2010/06/14)
-
- Sodium bis(trimethylsilyl)amide in the oxidative conversion of aldehydes to nitriles
-
The feasibility of the Me3Si species acting as a nucleofuge was investigated in compounds containing the NSiMe3 moiety. Treatment of various aromatic aldehydes with 2.2 equiv. of NaN(SiMe3)2 at 185°C in a sealed tube produced the corresponding nitriles in high yields (81-98%). In these reactions, NaN(SiMe3)2 acted as an oxidizing agent. Results from control experiments indicate that the Me 3Si unit can depart efficiently from the NSiMe3 moiety of N-silylimine intermediates. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Jih, Ru Hwu,Fung, Fuh Wong
-
p. 2513 - 2516
(2007/10/03)
-
- Light-initiated and thermal nitration reactions during photolysis of naphthalene/tetranitromethane or 1-methoxynaphthalene/tetranitromethane in dichloromethane
-
The photolysis of naphthalene or 1-methoxynaphthalene together with tetranitromethane in dichloromethane, using light with a cutoff at λ 2-promoted nitration (α/β ratio ca. 20). The adducts are formed by photochemical excitation of the CT complex between naphthalene and tetranitromethane, resulting in formation of the triad [ArH?+ NO2 (NO2)3C-] from which the observed chemistry develops by attack of trinitromethanide upon the radical cation. For 1-methoxynaphthalene, a representative of more highly reactive aromatics, the reaction is again photochemically initiated and again adducts seem to be responsible for the further development of thermal nitration reactions, apart from the NO2-induced reaction. Elimination of HNO2 from one of the 1,4-adducts induces a novel HNO2/tetranitromethane-dependent nitration process, shown separately to operate in the dark on reactive substrates. The aryltrinitromethane formed in this step is "hydrolyzed" to the corresponding carboxylic acid, 4-methoxy-1-naphthoic acid, under the anhydrous conditions prevailing during photolysis. Nitrous acid is a likely candidate as the proton source for this reaction. With an alcohol present, moderate yields (up to ≈50%) of alkyl 4-methoxy-1-naphthoates are obtained. From other adducts, nitro compounds are formed by elimination of nitroform. Trinitromethanide ion was shown to possess greatly differing reactivity (ratio >103) toward a model radical cation, tris(4-bromophenyl)aminium ion, in dichloromethane and acetonitrile, respectively.
- Eberson, Lennart,Radner, Finn
-
p. 5825 - 5834
(2007/10/02)
-
- Photosubstitution of 1-Methoxy-4-nitronaphthalene with Amine Nucleophiles: Dual Pathways
-
The photosubstitution of 1-methoxy-4-nitronaphthalene (MNN) with amines has been investigated by a combination of continuous and time-resolved experiments.Primary amines cause replacement of the nitro group, while secondary amines displace the methoxy substituent.Both reactions involve attack of the amine upon the triplet excited state of MNN.Spectroscopic evidence for the radical anion MNN*- has been obtained; the yield of this species depends upon the structure of the amine in the order RNH2*-, but that the reaction with primary amines is most probably an example of an SN2 Ar* process.The results for MNN and related compounds are discussed in the context of the orientation rules proposed by Mutai et al.
- Bunce, Nigel J.,Cater, Stephen R.,Scaiano, J. C.,Johnston, Linda J.
-
p. 4214 - 4223
(2007/10/02)
-
- Photochemical Reactions of Aromatic Compounds. Part 34. Direct Photocyanation of Arenes with Sodium Cyanide in the Presence of Electron Acceptors
-
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
-
p. 746 - 750
(2007/10/02)
-