- Rapid and Simple Access to α-(Hetero)arylacetonitriles from Gem-Difluoroalkenes
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A scalable cyanation of gem-difluoroalkenes to (hetero)arylacetonitrile derivatives was developed. This strategy features mild reaction conditions, excellent yields, wide substrate scope, and broad functional group tolerance. Significantly, in this reacti
- Hu, Dandan,Liu, Jiayue,Ren, Hongjun,Song, Jinyu,Zhang, Jun-Qi,Zhu, Guorong
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supporting information
p. 786 - 790
(2022/01/28)
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- From Stoichiometric Reagents to Catalytic Partners: Selenonium Salts as Alkylating Agents for Nucleophilic Displacement Reactions in Water
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The ability of chalcogenium salts to transfer an electrophilic moiety to a given nucleophile is well known. However, up to date, these reagents have been used in stoichiometric quantities, producing a substantial amount of waste as byproducts of the reaction. In this report, we disclose further investigation of selenonium salts as S-adenosyl-L-methionine (SAM) surrogates for the alkylation of nucleophiles in aqueous solutions. Most importantly, we were able to convert the stoichiometric process to a catalytic system employing as little as 10 mol % of selenides to accelerate the reaction between benzyl bromide and other alkylating agents with sodium cyanide in water. Probe experiments including 77Se NMR and HRMS of the reaction mixture have unequivocally shown the presence of the selenonium salt in the reaction mixture. (Figure presented.).
- Martins, Nayara Silva,ángel, Alix Y. Bastidas,Anghinoni, Jo?o M.,Lenard?o, Eder J.,Barcellos, Thiago,Alberto, Eduardo E.
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supporting information
p. 87 - 93
(2021/11/03)
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- Assembly of α-(Hetero)aryl Nitriles via Copper-Catalyzed Coupling Reactions with (Hetero)aryl Chlorides and Bromides
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α-(Hetero)aryl nitriles are important structural motifs for pharmaceutical design. The known methods for direct synthesis of these compounds via coupling with (hetero)aryl halides suffer from narrow reaction scope. Herein, we report that the combination of copper salts and oxalic diamides enables the coupling of a variety of (hetero)aryl halides (Cl, Br) and ethyl cyanoacetate under mild conditions, affording α-(hetero)arylacetonitriles via one-pot decarboxylation. Additionally, the CuBr/oxalic diamide catalyzed coupling of (hetero)aryl bromides with α-alkyl-substituted ethyl cyanoacetates proceeds smoothly at 60 °C, leading to the formation of α-alkyl (hetero)arylacetonitriles after decarboxylation. The method features a general substrate scope and is compatible with various functionalities and heteroaryls.
- Chen, Ying,Xu, Lanting,Jiang, Yongwen,Ma, Dawei
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supporting information
p. 7082 - 7086
(2021/02/26)
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- Density functional theory calculations, vibration spectral analysis and molecular docking of the antimicrobial agent 6-(1,3-benzodioxol-5-ylmethyl)-5-ethyl-2-{[2-(morpholin-4-yl)ethyl] sulfanyl}pyrimidin-4(3H)-one
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Vibrational spectral analysis and quantum chemical computations based on density functional theory have been performed on the antimicrobial agent 6-(1,3-benzodioxol-5-ylmethyl)-5-ethyl-2-{[2-(morpholin-4-yl)ethyl]sulfanyl}pyrimidin-4-(3H)-one. The equilibrium structural geometry, various bonding features and harmonic vibrational wavenumbers of the title compound have been investigated using DFT-B3LYP function at 6-311++G(d,p) basis set. The detailed interpretations of the vibrational spectra have been carried out with the aid of VEDA 4 program. The various intramolecular interactions of the title compound have been exposed by natural bond orbital analysis. The FT-IR and FT-Raman spectra of the title molecule have been recorded and analyzed. Blue-shifting of the C-H wavenumber along with a decrease in the C-H bond length attribute for the formation of the C-H...O hydrogen bonding provide an evidence for a charge transfer interaction. Also, the distribution of natural atomic charges reflects the presence of intramolecular hydrogen bonding. The analysis of the electron density of HOMO and LUMO gives an idea of the delocalization and the low value of energy gap indicates electron transfer within the molecule. Moreover, molecular docking studies revealed the possible binding of the title molecule to different antimicrobial target proteins.
- Almutairi, Maha S.,Soumya,Al-Wabli, Reem I.,Hubert Joe,Attia, Mohamed I.
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p. 653 - 666
(2020/03/30)
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- Copper-Catalyzed Cyanation of N-Tosylhydrazones with Thiocyanate Salt as the "cN" Source
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A novel protocol for the synthesis of α-aryl nitriles has been successfully achieved via a copper-catalyzed cyanation of N-tosylhydrazones employing thiocyanate as the source of cyanide. The features of this method include a convenient operation, readily available substrates, low-toxicity thiocyanate salts, and a broad substrate scope.
- Huang, Yubing,Yu, Yue,Zhu, Zhongzhi,Zhu, Chuanle,Cen, Jinghe,Li, Xianwei,Wu, Wanqing,Jiang, Huanfeng
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p. 7621 - 7627
(2017/07/26)
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- Two-step cyanomethylation protocol: Convenient access to functionalized aryl- and heteroarylacetonitriles
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A two-step protocol has been developed for the introduction of cyanomethylene groups to metalated aromatics through the intermediacy of substituted isoxazoles. A palladium-mediated cross-coupling reaction was used to introduce the isoxazole unit, followed by release of the cyanomethylene function under thermal or microwave-assisted conditions. The intermediate isoxazoles were shown to be amenable to further functionalization prior to deprotection of the sensitive cyanomethylene motif, allowing access to a wide range of aryl- and heteroaryl-substituted acetonitrile building blocks.
- Lindsay-Scott, Peter J.,Clarke, Aimee,Richardson, Jeffery
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supporting information
p. 476 - 479
(2015/03/05)
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- Enantioselective synthesis of amaryllidaceae alkaloids (+)-vittatine, (+)-epi-vittatine, and (+)-buphanisine
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Cat. on a hot tin roof: Enantioselective catalytic Michael addition of α-cyanoketones to acrylates under bifunctional organocatalysis was used to construct the unique arylic all-carbon quaternary stereocenter, which is synthetically crucial in the chemical synthesis of optically pure cis-aryl hydroindole alkaloids. The protocol offers an asymmetric route to (+)-vittatine, (+)-epi-vittatine, and (+)-buphanisine. Copyright
- Wei, Meng-Xue,Wang, Cheng-Tao,Du, Ji-Yuan,Qu, Hu,Yin, Pei-Rong,Bao, Xu,Ma, Xiao-Yan,Zhao, Xian-He,Zhang, Guo-Biao,Fan, Chun-An
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supporting information
p. 1966 - 1971
(2013/09/23)
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- Copper-catalyzed cyanation of benzyl chlorides with non-toxic K 4[Fe(CN)6]
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Copper-based catalysts were firstly introduced into the cyanation of benzyl chlorides with non-toxic K4[Fe(CN)6]. The presented method avoids the use of extremely poisonous alkali cyanides and precious palladium catalysts. No other reagent apart from CuI, K4[Fe(CN) 6] and toluene was used in the cyanation, showing that the presented protocol is simple and practical. A series of benzyl chlorides were smoothly cyanated in up to 85% yield under the optimal conditions.
- Ren, Yunlai,Dong, Chuanhua,Zhao, Shuang,Sun, Yanpei,Wang, Jianji,Ma, Junying,Hou, Chaodong
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supporting information; experimental part
p. 2825 - 2827
(2012/07/17)
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- Synthesis of α-Aryl nitriles through palladium-catalyzed decarboxylative coupling of cyanoacetate salts with aryl halides and triflates
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Worth its salt: The palladium-catalyzed decarboxylative coupling of the cyanoacetate salt as well as its mono- and disubstituted derivatives with aryl chlorides, bromides, and triflates is described (see scheme). This reaction is potentially useful for the preparation of a diverse array of α-aryl nitriles and has good functional group tolerance. S-Phos=2-(2,6- dimethoxybiphenyl)dicyclohexylphosphine), Xant-Phos=4,5-bis(diphenylphosphino)- 9,9-dimethylxanthene. Copyright
- Shang, Rui,Ji, Dong-Sheng,Chu, Ling,Fu, Yao,Liu, Lei
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supporting information; experimental part
p. 4470 - 4474
(2011/06/24)
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- A Selective and Mild Oxidation of Primary Amines to Nitriles with Trichloroisocyanuric Acid
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An efficient and highly selective method for the oxidative conversion of primary amines to the corresponding nitriles using trichloroisocyanuric acid in the presence of catalytic TEMPO under mild reaction conditions is described. Other functional groups such as C,C-double bonds, benzyloxy etc. were found to be unaffected under the reaction conditions. This procedure provides a new entry to the synthesis of various aliphatic, aromatic and heterocyclic nitriles in excellent yield.
- Chen, Fen-Er,Kuang, Yun-Yan,Dai, Hui-Fang,Lu, Liang,Huo, Ming
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p. 2629 - 2631
(2007/10/03)
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- Design, synthesis and antiproliferative activity of tripentones: A new series of antitubulin agents
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Structure-activity relationship studies of a new series of tripentones (thieno[2,3-b]pyrrolizin-8-ones), led us to prepare several derivatives with antiproliferative activities. The most promising 3-(3-hydroxy-4-methoxyphenyl)thieno[2,3-b]pyrrolizin-8-one 20 (leukemia L1210, IC50 = 15 nM) was shown to be a potent inhibitor of tubulin polymerization.
- Lisowski, Vincent,Enguehard, Cecile,Lancelot, Jean-Charles,Caignard, Daniel-Henri,Lambel, Stephanie,Leonce, Stephane,Pierre, Alain,Atassi, Ghanem,Renard, Pierre,Rault, Sylvain
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p. 2205 - 2208
(2007/10/03)
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- The reduction of α,β-unsaturated nitriles and α-halonitriles with sodium hydrogen telluride
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Sodium hydrogen telluride reacts chemoselectively with α,β- unsaturated nitriles and α-halonitriles linked to aromatic and aliphatic substituents to corresponding saturated nitriles with good yields.
- Blay, Gonzalo,Cardona, Luz,Garcia, Begona,Lahoz, Luisa,Pedro, Jose R.
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p. 8611 - 8618
(2007/10/03)
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- SYNTHESES BASED ON β-PHENYLETHYLAMINES. I. PREPARATION OF SUBSTITUTED β-PHENYLETHYLAMINES
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A comparative study has been made of methods of synthesizing substituted β-phenylethylamines via the corresponding nitriles and via nitrostyrenes, and a superiority of the latter method has been established.The possibility has been shown for the first time of reducing nitrostyrenes to saturated amines with diisobutylaluminum hydride (DIBAH).The use of DIBAH as reducing agent enables amines to be obtained in high yields.
- Vinogradova, V. I.,Yunusov, M. S.,Kuchin, A. V.,Tolstikov, G. A.,Sagandykov, R. T.,et al.
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- A Facile Synthesis of Nitriles from 1-Nitro-1-alkenes by Electroreduction
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Electroreduction of 1-nitro-1-alkenes in the presence of titanium(IV) chloride affords nitriles in good yields.This procedure provides a facile transformation of aldehydes to one-carbon elongated nitriles since the 1-nitro-1-alkenes are best prepared from aldehydes and nitromethane.
- Sera, Akira,Tani, Hiroyuki,Nishiguchi, Ikuzo,Hirashima, Tsuneaki
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p. 631 - 633
(2007/10/02)
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- A SIMPLE ONE-POT CONVERSION OF ARYL HALIDES INTO ARYLACETONITRILES
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When heated in hexamethylphosphoric triamide in the presence of copper(I) iodide, aryl iodides and bromides react with cyanoacetate anion to form arylcyanoacetates, which lose the ester group on hydrolysis, giving the corresponding arylacetonitriles in good to moderate yields.
- Suzuki, Hitomi,Kobayashi, Tsutomu,Yoshida, Yoshiki,Osuka, Atsuhiro
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p. 193 - 194
(2007/10/02)
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- Syntheses of Arylacetone and Arylacetonitrile by Friedel-Crafts Reaction with α-Chloro-α-(methylthio)-substituted Acetone and Acetonitrile
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Novel preparative methods for arylacetone and arylacetonitrile are described.Friedel-Crafts reactions of aromatic compounds with α-chloro-α-(methylthio)acetone (4) and α-chloro-α-(methylthio)acetonitrile (7) in the presence of Lewis acid afforded α-(methylthio)arylacetone (5) and α-(methylthio)arylacetonitrile (8), respectively.Compounds (5) and (8) were converted into the corresponding arylacetone (6) and arylacetonitrile (9) by reduction with zinc dust in acetic acid.Keywords: Friedel-Crafts reaction with α-chloro-α-(methylthio)acetone; Friedel-Crafts reaction with α-chloro-α-(methylthio)acetonitrile; α-(methylthio)arylacetone; α-(methylthio)arylacetonitrile; arylacetone; arylacetonitrile; reductive desulfurization; zinc dust-acetic acid
- Tamura, Yasumitsu,Choi, Hong Dae,Mizutani, Masako,Ueda, Yuko,Ishibashi, Hiroyuki
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p. 3574 - 3579
(2007/10/02)
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