- Sonocatalyzed synthesis of 2-phenylvaleronitrile under controlled reaction conditions - A kinetic study
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In the current study, kinetics of synthesis of 2-phenylvaleronitrile (PVN) was successfully carried out by selective C-alkylation of benzyl cyanide (BC) with n-bromopropane (BP) using aqueous KOH and catalyzed by TBAB under ultrasonic (300 W) assisted org
- Vivekanand,Wang, Maw-Ling
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- Cu-Catalyzed alkylation-cyanation type difunctionalization of styrenes with aliphatic aldehydes and TMSCN via decarbonylation
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A copper-catalyzed decarbonylative alkylation-cyanation of styrene derivatives with aliphatic aldehydes and trimethylsilyl cyanide to provide chain elongated nitriles is reported. Using TBHP as an oxidant and free radical initiator, the reaction can smoothly convert abundant α-di-substituted, α-mono-substituted and linear aliphatic aldehydes into the corresponding 3°, 2° and 1° alkyl radicals to initiate the subsequent radical-type difunctionalization of various styrenes.
- Zhou, Yu-Ling,Chen, Jun-Jia,Cheng, Jing,Yang, Luo
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supporting information
p. 1231 - 1235
(2022/02/19)
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- Ni-Catalyzed Isomerization-Hydrocyanation Tandem Reactions: Access to Linear Nitriles from Aliphatic Internal Olefins
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A highly regioselective nickel-based catalyst system for the isomerization/hydrocyanation of aliphatic internal olefins is described. This benign tandem reaction provides facile access to a wide variety of aliphatic nitriles in good yields with excellent regioselectivities. Thanks to Lewis acid-free conditions, the protocol features board functional groups tolerance, including secondary amine and unprotected alcohol groups.
- Gao, Jihui,Ni, Jie,Yu, Rongrong,Cheng, Gui-Juan,Fang, Xianjie
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supporting information
p. 486 - 490
(2021/02/05)
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- Base-controlled chemoselectivity: direct coupling of alcohols and acetonitriles to synthesise α-alkylated arylacetonitriles or acetamides
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We achieved chemoselective synthesis of α-alkylated arylacetonitriles and acetamides by combining Ir complex-catalysed direct coupling of alcohols and nitriles by a simple adjustment of the base. Methanol and ethanol performed well as the alkylating reagents. This method of acetonitrile alkylation provided a novel approach for carbon chain extension.
- Bai, Liang,Ge, Min-Tong,Li, Chen,Qiu, Yuan-Rui,Wang, Ying,Xia, Ai-Bao,Xu, Dan-Qian
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supporting information
p. 15200 - 15204
(2021/09/06)
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- Ni-Catalyzed hydrocyanation of alkenes with formamide as the cyano source
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CN generation from formamide dehydration! A novel Ni-catalyzed hydrocyanation of various alkenes to provide aliphatic nitriles is developed by generating hydrocyanic acid in situ from safe and readily available formamide. Excellent linear or branched regio-selectivity, wide substrate scope, cheap and stable nickel salt as a pre-catalyst, a safe cyano source, slow generation of CN to obviate catalyst deactivation and convenient experimental operation would render this hydrocyanation attactive for laboratory synthesis of aliphatic nitriles.
- Shu, Xiao,Jiang, Yuan-Yuan,Kang, Lei,Yang, Luo
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supporting information
p. 2734 - 2738
(2020/06/17)
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- Enantioseparation of Sulfoxides and Nitriles by Inclusion Crystallization with Chiral Organic Salts Based on l-Phenylalanine
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Enantioselective inclusion of aromatic sulfoxides and nitriles was achieved in a host framework created by organic salts comprising achiral benzoic acids and a chiral primary amine (1a) derived from l-phenylalanine. Tuning of the combined achiral acid component successfully changed the chiral recognition ability of the organic salts. The guest molecules were hydrogen-bonded to form three-component inclusion crystals, and the enantiomers of nitriles and sulfoxides were separated with high selectivity up to 92 and 98 % ee. As far as we know, this is the first example of the enantioseparation of non-functionalized aromatic nitriles.
- Kodama, Koichi,Kanai, Hayato,Shimomura, Yuki,Hirose, Takuji
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supporting information
p. 1726 - 1729
(2018/04/24)
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- Facile Ruthenium(II)-Catalyzed α-Alkylation of Arylmethyl Nitriles Using Alcohols Enabled by Metal-Ligand Cooperation
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A facile ruthenium(II)-catalyzed α-alkylation of arylmethyl nitriles using alcohols is reported. The ruthenium pincer catalyst serves as an efficient catalyst for this atom-economical transformation that undergoes alkylation via borrowing hydrogen pathways, producing water as the only byproduct. Arylmethyl nitriles containing different substituents can be effectively alkylated using diverse primary alcohols. Notably, using ethanol and methanol as alkylating reagents, challenging ethylation and methylation of arylmethyl nitriles were performed. Secondary alcohols do not undergo alkylation reactions. Thus, phenylacetonitrile was chemoselectively alkylated using primary alcohols in the presence of secondary alcohols. Diols provided a mixture of products. When deuterium-labeled alcohol was used, the expected deuterium transposition occurred, providing both α-alkylation and α-deuteration of arylmethyl nitriles. Consumption of nitrile was monitored by GC, which indicated the involvement of first-order kinetics. Plausible mechanistic pathways are suggested on the basis of experimental evidence. The ruthenium catalyst reacts with base and generates an unsaturated intermediate, which further reacts with both nitriles and alcohols. While nitrile is transformed to enamine via [2 + 2] cycloaddition, alcohol is oxidized to aldehyde. The metal bound enamine adduct reacts with aldehyde via Michael addition, resulting in an ene-imine adduct, which perhaps undergoes direct hydrogenation by a Ru dihydride intermediate, produced from alcohol oxidation. However, in situ monitoring of the reaction mixture confirmed the presence of unsaturated vinyl nitrile in the reaction mixture in minor amounts (10%), indicating the possible dissociation of ene-imine adduct during the catalysis, which may further be hydrogenated to provide the α-alkylated nitriles. Overall, the efficient α-alkylation of nitriles using alcohols can be attributed to the amine-amide metal-ligand cooperation that is operative in the ruthenium pincer catalyst, which enables all of the catalytic intermediates to remain in the +2 oxidation state throughout the catalytic cycle.
- Thiyagarajan, Subramanian,Gunanathan, Chidambaram
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p. 5483 - 5490
(2017/08/17)
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- Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols
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The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen.
- Li, Junjun,Liu, Yuxuan,Tang, Weijun,Xue, Dong,Li, Chaoqun,Xiao, Jianliang,Wang, Chao
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supporting information
p. 14445 - 14449
(2017/10/07)
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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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- Photoinduced direct cyanation of C(sp3)-H bonds
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A general and practical synthetic protocol for the direct transformation of unreactive C(sp3)-H bonds to C(sp3)-CN bonds has been developed. The homolytic cleavage of the C-H bond is initiated by photo-excited benzophenone, and the resulting carbon radical subsequently reacts with tosyl cyanide to afford the corresponding nitrile in a highly efficient manner. The present methodology is widely applicable to various starting materials including ethers, alcohols, amine derivatives, alkanes, and alkylbenzenes. This newly developed C-H cyanation protocol provides a powerful tool for selective one-carbon elongation for the construction of architecturally complex molecules. Georg Thieme Verlag Stuttgart - New York.
- Hoshikawa, Tamaki,Yoshioka, Shun,Kamijo, Shin,Inoue, Masayuki
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p. 874 - 887
(2013/05/09)
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- Photochemically induced radical transformation of C(sp3)-H bonds to C(sp3)-CN bonds
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A general protocol for direct transformation of unreactive C(sp 3)-H bonds to C(sp3)-CN bonds has been developed. The C-H activation was effected by photoexcited benzophenone, and the generated carbon radical was subsequently trapped with tosyl cyanide to afford the corresponding nitrile in a highly efficient manner. The present methodology is widely applicable to versatile starting materials and, thus, serves as a powerful tool for selective one-carbon elongation for construction of architecturally complex molecules.
- Kamijo, Shin,Hoshikawa, Tamaki,Inoue, Masayuki
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supporting information; experimental part
p. 5928 - 5931
(2011/12/21)
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- Novel α-arylnitriles synthesis via Ni-catalyzed cross-coupling of α-bromonitriles with arylboronic acids under mild conditions
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An applicable and easy-handling Ni-catalyst can be used to promote direct arylation of α-bromonitriles with various arylboronic acids to construct α-arylnitriles under mild conditions. The methodology tolerates β-hydrogens and functional groups in the substrates.
- Yang, Yingying,Tang, Shan,Liu, Chao,Zhang, Huimin,Sun, Zhexun,Lei, Aiwen
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supporting information; scheme or table
p. 5343 - 5345
(2011/09/13)
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- Synthesis of 3,3-and 4,4-alkyl-phenyl-substituted pyrrolidin-2-one derivatives
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Syntheses of 3,3-and 4,4-alkyl-phenyl-substituted pyrrolidin-2-one derivatives are described. The final compounds were obtained by the reductive cyclization of relevant cyanoalkanoate esters using NaBH4 and CoCl2.6H2O. The obtained pyrroIidin-2-one derivatives are pharmacophoric fragments for the synthesis of various biologically active compounds.
- Kulig,Ignasik,Malawska
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scheme or table
p. 1629 - 1636
(2010/07/06)
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- How iodide anions inhibit the phase-transfer catalyzed reactions of carbanions
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The inhibitory effect of iodide anions on the phase-transfer catalyzed reactions of carbanions generated in liquid-liquid two-phase systems by aqueous NaOH is due to preferential location of these anions in the interfacial region of the two-phase system-organic phase/concd aqueous NaOH. In such situation, the basic activity of NaOH in this region is decreased and the equilibrium of deprotonation of the carbanion precursors is disfavoured.
- Makosza, Mieczys?aw,Chesnokov, Alexey
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p. 5925 - 5932
(2008/12/20)
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- Oxidative conversion of α,α-disubstituted acetamides to corresponding one-carbon-shorter ketones using hypervalent iodine (λ5) reagents in combination with tetraethylammonium bromide
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(Chemical Equation Presented) α,α-Disubstituted acetamides undergo oxidative dehomologation to give one-carbon-shorter ketones when reacted with a hypervalent iodine (λ5) reagent in combination with tetraethylammonium bromide (TEAB) in various solvents. In further studies, one such combination of a hypervalent iodine (λ5) reagent, o-iodoxybenzoic acid, and TEAB has been established as a new, mild, efficient, and general method for the transformation.
- Bellale, Eknath V.,Bhalerao, Dinesh S.,Akamanchi, Krishnacharya G.
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supporting information; experimental part
p. 9473 - 9475
(2009/04/06)
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- Facile one-pot synthesis of 2-aryl-substituted nitriles and 2-aryl-3-keto nitriles via benzyne reaction
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2-Aryl-substituted nitriles were prepared in good to excellent yields in a one-pot reaction by the reaction of benzyne, generated using neutral conditions from (phenyl)[o-(trimethylsilyl)-phenyl]iodonium triflate, and 2-lithionitriles. 3-Keto nitriles substituted at the 2-position were obtained in good yields when these reactions were trapped with acid chlorides. The mechanism of the benzyne reaction in terms of a N-lithiobenzocyclobutanimine intermediate is discussed. Copyright Taylor & Francis Group, LLC.
- Kamila, Sukanta,Koh, Benjamin,Biehl, Edward R.
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p. 3493 - 3507
(2007/10/03)
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- Synthesis of alkylaryl-and diarylnitriles from ketones via N-(1- arylalkylidene)-cyanomethyl amines
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Alkylaryl- and diarylketones (Arcor; R= alkyl, aryl, 1) can be converted into nitriles [ArCH(CN)R, 2] containing an additional carbon atom through a base-promoted reaction of N-(1-arylalkylidene)-cyanomethyl amines [ArC(=NCH2CN)R, 3].
- Selva, Maurizio,Bomben, Andrea,Tundo, Pietro
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p. 1561 - 1569
(2007/10/03)
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- Molecular Orbital and Experimental Studies on the Photoinduced Decarboxylation of Pyrethroid Model Esters
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A series of pyrethroid model esters with various substituents in the acid or alcohol moiety have been irradiated by u. v.-radiation (λ > 220 nm).The main reaction is decarboxylation, as evidenced by gas chromatographic (g. c.) and mass spectrometric (m. s.) analyses.In the photoinduced decarboxylation reaction, the substituent effect on the main transition, which occurs via carbonyl excitation, and on the reactivity of a radical intermediate have been examined by semiempirical molecular-orbital calculations (MNDO and CNDO/S).It has been found tha the change of benzyl carbon-oxygen bond strength in the excited states is one of the important factors in determining the yield of the decarboxylated product.
- Katagi, Toshiyuki,Mikami, Nobuyoshi,Matsuda, Tadashi,Miyamoto, Junshi
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p. 779 - 782
(2007/10/02)
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- Aromatase Inhibitors. Synthesis and Evaluation of Mammary Tumor Inhibiting Activity of 3-Alkylated 3-(4-Aminophenyl)piperidine-2,6-diones
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The synthesis and biological evaluation of 3-alkyl-substituted 3-(4-aminophenyl)piperidine-2,6-diones as inhibitors of estrogen biosynthesis are described .In vitro compounds 4-14 showed a stronger inhibition of human placental aromatase compared to aminoglutethimide (AG, compound 3), which recently has become used for the treatment of hormone-dependent breast cancer.The most active derivative, compound 10, showed a 93-fold stronger inhibition than AG.With the exception of 5, 7, and 8, all other compounds exhibited similar or decreased inhibition of bovine adrenal desmolase compared to AG.Compounds 4 and 6-12 showed a stronger inhibition of the plasma estradiol concentration of pregnant mare serum gonadotropin (PMSG) primed Sprague-Dawley (SD) rats compared to the parent compound.Compounds 4, 6-8, 10, and 12 inhibited the testosterone-stimulated tumor growth of ovariectomized 9,10-dimethyl-1,2-benzanthracene (DMBA) tumor-bearing SD rats more strongly than AG.Being stronger and more selective inhibitors of the estrogen biosynthesis than AG, some of the newly developed derivatives of AG might be better candidates for the treatment of the hormone-dependent human breast cancer.
- Hartmann, Rolf W.,Batzl, Christine
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p. 1362 - 1369
(2007/10/02)
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- SELECTIVE alpha -MONOALKYLATION OF PHENYLACETONITRILE USING ALKALI METAL HYDROXIDE IMPREGNATED ON ALUMINA.
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In the alkylation of phenylacetonitrile with alkyl halides, alkali metal hydroxides impregnated on alumina act as efficient bases for selective alpha -monoalkylation in benzene. It is proposed that the reaction may take place exclusively in the pore. The selectivity for alpha -monoalkylation is explained in terms of steric hindrance.
- Sukata
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p. 3306 - 3307
(2007/10/02)
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- Oxidative Decyanation of Secondary Nitriles to Ketones
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Procedures for the oxidative decyanation of secondary nitriles to ketones involve (1) iodination of N-(trialkylsilyl)ketenimines derived from secondary nitriles and subsequent hydrolysis of the α-iodo nitriles with silver oxide, (2) addition of nitrosobenzene to N-(trialkylsilyl)ketenimines, (3) conversion of secondary nitriles to α-(phenylthio) nitriles and subsequent hydrolysis with N-bromosuccinimide in aqueous acetonitrile, and (4) preparation of α-hydroperoxy nitriles by direct oxygenation of anions of secondary nitriles and subsequent reductive hydrolysis with stannous chloride followed by sodium hydroxide.The latter general procedure was applied to various secondary nitriles bearing dialkyl, aryl and alkyl, and diaryl substituents to provide ketones in good yield and was extended to the oxidative decyanation of α,β-unsaturated nitriles to furnish α,β-unsaturated ketones.
- Freerksen, Robert W.,Selikson, Sandra J.,Wroble, Randall R.,Kyler, S. Keith,Watt, David S.
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p. 4087 - 4096
(2007/10/02)
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