3058-39-7Relevant articles and documents
Revealing resonance effects and intramolecular dipole interactions in the positional isomers of benzonitrile-core thermally activated delayed fluorescence materials
Kukhta, Nadzeya A.,Higginbotham, Heather F.,Matulaitis, Tomas,Danos, Andrew,Bismillah, Aisha N.,Haase, Nils,Etherington, Marc K.,Yufit, Dmitry S.,McGonigal, Paul R.,Gra?ulevi?ius, Juozas Vidas,Monkman, Andrew P.
, p. 9184 - 9194 (2019)
We report on the properties of the three positional isomers of (2,7-di-tert-butyl-9,9-dimethylacridin-10(9H)-yl)benzonitrile, which are found to have comparable donor steric environments and donor-acceptor dihedral angles. An unexpected intramolecular dip
Nitrile Synthesis via Desulfonylative-Smiles Rearrangement
Abe, Masahiro,Nitta, Sayasa,Miura, Erina,Kimachi, Tetsutaro,Inamoto, Kiyofumi
, p. 4460 - 4467 (2022/03/15)
Herein, we designed a simple nitrile synthesis from N-[(2-nitrophenyl)sulfonyl]benzamides via base-promoted intramolecular nucleophilic aromatic substitution. The process features redox-neutral conditions as well as no requirement of toxic cyanide species and transition metals. Our process shows broad scope and various functional group compatibility, affording a variety of (hetero)aromatic nitriles in good to excellent yields.
Photoinduced Acetylation of Anilines under Aqueous and Catalyst-Free Conditions
Yang, Yu-Ming,Yan, Wei,Hu, Han-Wei,Luo, Yimin,Tang, Zhen-Yu,Luo, Zhuangzhu
, p. 12344 - 12353 (2021/09/02)
A green and efficient visible-light induced functionalization of anilines under mild conditions has been reported. Utilizing nontoxic, cost-effective, and water-soluble diacetyl as photosensitizer and acetylating reagent, and water as the solvent, a variety of anilines were converted into the corresponding aryl ketones, iodides, and bromides. With advantages of environmentally friendly conditions, simple operation, broad substrate scope, and functional group tolerance, this reaction represents a valuable method in organic synthesis.
Palladium-Catalyzed Decarbonylative Iodination of Aryl Carboxylic Acids Enabled by Ligand-Assisted Halide Exchange
Boehm, Philip,Cacherat, Bastien,Lee, Yong Ho,Martini, Tristano,Morandi, Bill
supporting information, p. 17211 - 17217 (2021/07/02)
We report an efficient and broadly applicable palladium-catalyzed iodination of inexpensive and abundant aryl and vinyl carboxylic acids via in situ activation to the acid chloride and formation of a phosphonium salt. The use of 1-iodobutane as iodide source in combination with a base and a deoxychlorinating reagent gives access to a wide range of aryl and vinyl iodides under Pd/Xantphos catalysis, including complex drug-like scaffolds. Stoichiometric experiments and kinetic analysis suggest a unique mechanism involving C?P reductive elimination to form the Xantphos phosphonium chloride, which subsequently initiates an unusual halogen exchange by outer sphere nucleophilic substitution.
Cu2O-Catalyzed Conversion of Benzyl Alcohols Into Aromatic Nitriles via the Complete Cleavage of the C≡N Triple Bond in the Cyanide Anion
Liu, Wenbo,Tang, Peichen,Zheng, Yi,Ren, Yun-Lai,Tian, Xinzhe,An, Wankai,Zheng, Xianfu,Guo, Yinggang,Shen, Zhenpeng
, p. 3509 - 3513 (2021/10/04)
Nitrogen transfer from cyanide anion to an aldehyde is emerging as a promising method for the synthesis of aromatic nitriles. However, this method still suffers from a disadvantage that a use of stoichiometric Cu(II) or Cu(I) salts is required to enable the reaction. As we report herein, we overcame this drawback and developed a catalytic method for nitrogen transfer from cyanide anion to an alcohol via the complete cleavage of the C≡N triple bond using phen/Cu2O as the catalyst. The present condition allowed a series of benzyl alcohols to be smoothly converted into aromatic nitriles in moderate to high yields. In addition, the present method could be extended to the conversion of cinnamic alcohol to 3-phenylacrylonitrile.
Water-Dispersible Pd–N-Heterocyclic Carbene Complex Immobilized on Magnetic Nanoparticles as a New Heterogeneous Catalyst for Fluoride-Free Hiyama, Suzuki–Miyaura and Cyanation Reactions in Aqueous Media
Chahkamali, Farhad Omarzehi,Sansano, José Miguel,Sobhani, Sara
, (2021/11/10)
Abstract: Pd–N-heterocyclic carbine complex immobilized on magnetic nanoparticles is synthesized and characterized by different techniques such as FT-IR, XPS, TEM, EDX, FESEM, VSM, TGA, and ICP. The synthesized catalyst was used as a new water dispersible heterogeneous catalyst in the fluoride-free Hiyama, Suzuki–Miyaura and cyanation reactions in pure water. By this method, different types of biaryls and aryl nitriles were synthesized in good to high yields by the reaction of a variety of aryl iodides, bromides and chlorides with triethoxyphenylsilane, phenylboronic acid and K4[Fe(CN)6]·3H2O, respectively. The presence of sulfonates as hydrophilic groups on the surface of the catalyst confers a highly water dispersible, active and yet magnetically recoverable Pd catalyst. The possibility to perform the reaction in water as a green medium, ease of the catalyst recovery and reuse by magnetic separation, and the absence of any additives or co-solvents make this method as an eco-friendly and economical protocol for the synthesis of biaryl derivatives and aryl nitriles. Graphic Abstract: A new water dispersible heterogeneous Pd–N-heterocyclic carbene for the efficient fluoride-free Hiyama, Suzuki–Miyaura and cyanation reactions in pure water is developed.[Figure not available: see fulltext.].
Pd@CeO2-catalyzed cyanation of aryl iodides with K4Fe(CN)6·3H2O under visible light irradiation
Wang, Shengyu,Wang, Jianqiang,Pan, Junyi,Liu, Cheng,Gong, Xubin,Guo, Cheng
, (2021/01/12)
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.
Highly Efficient Oxidative Cyanation of Aldehydes to Nitriles over Se,S,N-tri-Doped Hierarchically Porous Carbon Nanosheets
Hua, Manli,Song, Jinliang,Huang, Xin,Liu, Huizhen,Fan, Honglei,Wang, Weitao,He, Zhenhong,Liu, Zhaotie,Han, Buxing
supporting information, p. 21479 - 21485 (2021/08/23)
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.
Visible-Light-Promoted Metal-Free Synthesis of (Hetero)Aromatic Nitriles from C(sp3)?H Bonds**
Murugesan, Kathiravan,Donabauer, Karsten,K?nig, Burkhard
supporting information, p. 2439 - 2445 (2020/12/07)
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.
Nitrile Synthesis by Aerobic Oxidation of Primary Amines and in situ Generated Imines from Aldehydes and Ammonium Salt with Grubbs Catalyst
Utsumi, Tatsuki,Noda, Kenta,Kawauchi, Daichi,Ueda, Hirofumi,Tokuyama, Hidetoshi
supporting information, p. 3583 - 3588 (2020/08/05)
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.).
