- Enhancing catalytic performance via structure core-shell metal-organic frameworks
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A core-shell structure metal-organic framework based on the Zr clusters bridging with BDC linkers (UiO-66) as a core-structure and BPYDC linkers (UiO-67-BPY) as a shell-structure was developed (UiO-67-BPY@UiO-66). The combination of several techniques suc
- Gong, Yanyan,Yuan, Ye,Chen, Cheng,Zhang, Pan,Wang, Jichao,Khan, Anish,Zhuiykov, Serge,Chaemchuen, Somboon,Verpoort, Francis
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Read Online
- Stereoselective desymmetrizations of dinitriles to synthesize lactones
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Nitriles are important organic functional groups, allowing for installation of nitrogen in organic synthesis. The Pinner reaction transforms nitriles into esters via the imidate group, but in general has previously necessitated harsh acid conditions. This
- Baber, Tylisha M.,Bain, Schuyler A.,Caleb Lykins, T.,Frost, Joshua A.,Kelley, Amber M.,Michishita, Emiri,Petersen, Kimberly S.,Youngblood, Kala C.
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supporting information
(2021/12/17)
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- Catalyst-Free [3 + 3] Annulation/Oxidation of Cyclic Amidines with Activated Olefins: When the Substrate Olefin Is Also an Oxidant
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Herein we describe a catalyst-free regioselective [3 + 3] annulation/oxidation reaction of cyclic amidines such as DBU (1,8-diazabicyclo(5.4.0)undec-7-ene) and DBN (1,5-diazabicyclo(4.3.0)non-5-ene) with activated olefins, i.e., 2-arylidenemalononitriles and 2-cyano-3-aryl acrylates, to afford tricyclic 2-pyridones and pyridin-2(1H)-imines, respectively. The mechanism has been proposed based on DFT calculations. In the reaction, the cyclic amidines serve as C,N-bisnucleophiles for the cyclization, while the olefins play a dual role by acting as both reactants and oxidants.
- Han, Wendan,Li, Yuanhang,Raveendra Babu, Kaki,Li, Jing,Tang, Yuhai,Wu, Yong,Xu, Silong
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p. 7832 - 7841
(2021/06/25)
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- Direct Cyclopropanation of α-Cyano β-Aryl Alkanes by Light-Mediated Single Electron Transfer Between Donor–Acceptor Pairs
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Cyclopropanes are traditionally prepared by the formal [2+1] addition of carbene or radical based C1 units to alkenes. In contrast, the one-pot intermolecular cyclopropanation of alkanes by redox active C1 units has remained unrealised. Herein, we achieve
- Li, Jing,Lear, Martin J.,Hayashi, Yujiro
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p. 5901 - 5905
(2021/03/09)
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- Preparation of O-Protected Cyanohydrins by Aerobic Oxidation of α-Substituted Malononitriles in the Presence of Diarylphosphine Oxides
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A mild, reagent-cyanide-free, and efficient synthesis of O-phosphinoyl-protected cyanohydrins from readily available α-substituted malononitriles was realized using diarylphosphine oxides in the presence of O2. Mechanistic studies indicated that in addition to the initial aerobic oxidation of the malononitrile derivative notable features of this process include the formation of a tetrahedral intermediate and a subsequent intramolecular rearrangement. The phosphinoyl-protecting group can be removed by alcoholysis or by reduction with DIBAL-H.
- Zhang, Dapeng,Lian, Mingming,Liu, Jia,Tang, Shukun,Liu, Guangzhi,Ma, Cunfei,Meng, Qingwei,Peng, Haisheng,Zhu, Daling
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p. 2597 - 2601
(2019/04/17)
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- Synthesis and biocatalytic ene-reduction of Knoevenagel condensation compounds by the marine-derived fungus Penicillium citrinum CBMAI 1186
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The chemoselective bioreduction of α,β-unsaturated compounds is an important synthetic tool that can have applications in the synthesis of many fine chemicals and pharmaceutical molecules. The synthesis of aromatic malononitrile derivatives through Knoevenagel condensation by microwave radiation under green chemistry conditions using methanol like solvent, free base and free catalyst is here reported. In addiction the biocatalytic reduction of the C–C double bond of aromatic malononitrile derivatives by whole cells of the marine-derived fungal Penicillium citrinum CBMAI 1186 was also tested. The products catalyzed by the fungus ene-reductase were obtained in very good yields (up to >98%).
- Jimenez, David E.Q.,Ferreira, Irlon M.,Birolli, Willian G.,Fonseca, Luis P.,Porto, André L.M.
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p. 7317 - 7322
(2016/10/29)
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- Base-Promoted Cascade Approach for the Preparation of Reduced Knoevenagel Adducts Using Hantzsch Esters as Reducing Agent in Water
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A cascade Knoevenagel condensation-reduction approach, which was carried out in water, has been reported. Using Hantzsch esters as reducing agent, under the promotion of base, a variety of reduced Knoevenagel adducts could be easily prepared by direct alkylation of malononitrile, ethyl 2-cyanoacetate, and 2-(4-nitrophenyl)acetonitrile, respectively. Meanwhile, a gram-scale synthesis of the protocol was also realized with excellent isolated yield.
- He, Tao,Shi, Ronghua,Gong, Yimou,Jiang, Guangyou,Liu, Ming,Qian, Shan,Wang, Zhouyu
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supporting information
p. 1864 - 1869
(2016/07/16)
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- Discovery of mixed type thymidine phosphorylase inhibitors endowed with antiangiogenic properties: Synthesis, pharmacological evaluation and molecular docking study of 2-thioxo-pyrazolo[1,5-a][1,3,5]triazin-4-ones. Part II
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In our drug discovery program, a series of 2-thioxo-pyrazolo[1,5-a][1,3,5] triazin-4-ones were designed, synthesized and evaluated for their TP inhibitory potential. All the synthesized analogues conferred a varying degree of TP inhibitory activity, comparable or better than positive control, 7-deazaxanthine (7-DX, 2) (IC50 value = 42.63 μM). A systematic approach to the lead optimization identified compounds 3c and 4a as the most promising TP inhibitors, exhibiting mixed mode of enzyme inhibition. Moreover, selected compounds demonstrated the ability to attenuate the expression of the angiogenic markers (viz. MMP-9 and VEGF) in MDA-MB-231 cells at sublethal concentrations. In addition, molecular docking studies revealed the plausible binding orientation of these inhibitors towards TP, which was in accordance with the experimental results. Taken as a whole, these compounds would constitute a new direction for the design of novel TP inhibitors with promising antiangiogenic properties.
- Bera, Hriday,Ojha, Probir Kumar,Tan, Bee Jen,Sun, Lingyi,Dolzhenko, Anton V.,Chui, Wai-Keung,Chiu, Gigi Ngar Chee
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p. 294 - 303
(2014/04/17)
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- Study on comparison of reducing ability of three organic hydride compounds
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Selective reduction of three kinds of substrates were studied to evaluate the reducing abilities of N,N-dimethyl-benzimidazolidine (DMBI), 2-phenylbenzimidazoline (PBI) and 2-phenylbenzothiazoline (PBT). As hydride donors, these three five-membered heterocyclic compounds performed different reducing abilities depending on the substrates.
- Feng, Yi-Si,Yang, Chun-Yan,Huang, Qiang,Xu, Hua-Jian
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p. 5053 - 5059
(2012/07/28)
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- Rh-catalyzed one-pot reductive alkylation of malononitrile under transfer hydrogenation conditions
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Efficient synthesis of monosubstituted malononitriles was achieved by one-pot reductive alkylation of malononitrile with carbonyl compounds via [Cp*RhCl2]2-catalyzed transfer hydrogenation reaction.
- Wu, Jiashou,Jiang, Huajiang
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experimental part
p. 1218 - 1226
(2011/05/04)
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- Nanocrystalline ZnO for Knoevenagel condensation and reduction of the carbon, carbon double bond in conjugated alkenes
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A novel efficient and eco-friendly nanocrystalline ZnO catalyst was used for the Knoevenagel condensation and for the reduction of C=C double bonds at room temperature in the absence of solvents.
- Hosseini-Sarvari, Mona,Sharghi, Hashem,Etemad, Samane
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scheme or table
p. 715 - 724
(2009/02/07)
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- Monosubstituted malononitriles: Efficient one-pot reductive alkylations of malononitrile with aromatic aldehydes
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A powerful new one-pot method has been developed for the reductive alkylation of malononitrile with aromatic aldehydes. This new procedure has vastly improved the yield and efficiency of the process, and increased the scope of the aromatic aldehydes. Inco
- Tayyari, Fariba,Wood, Dwight E.,Fanwick, Phillip E.,Sammelson, Robert E.
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p. 279 - 285
(2008/12/22)
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- A facile experimental method to determine the hydride affinity of polarized olefins in acetonitrile
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(Chemical Equation Presented) Choosing a suitable hydride reducing agent and thermodynamic analysis of reduction mechanisms is facilitated by experimental hydride affinities ΔHH-A, which are reported herein for 28 polarized olefins 1 in acetonitrile (see scheme). The method should also be applicable to ketones, aldehydes, and imines.
- Zhu, Xiao-Qing,Zhang, Min,Liu, Qiao-Yun,Wang, Xiao-Xiao,Zhang, Jian-Yu,Cheng, Jin-Pei
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p. 3954 - 3957
(2007/10/03)
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- Solvent-free mechanochemical and one-pot reductive benzylizations of malononitrile and 4-methylaniline using Hantzsch 1,4-dihydropyridine as the reductantt
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The properties of Hantzsch 1,4-dihydropyridine, which possesses excellent reducibility, were investigated. The synthesis of benzyl malononitriles and anilines were also studied. Direct reductive benzylizations of malononitrile and 4-methylaniline by aromatic aldehydes were achieved using a Hantzsch 1,4-dihydropyridine as the reductant. It was observed that there is no need for the separation of the in situ generated benzylidene malononitriles and p-tolylamines.
- Zhang, Ze,Gao, Jie,Xia, Jing-Jing,Wang, Guan-Wu
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p. 1617 - 1619
(2007/10/03)
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- Efficient role of Mg-ZnCl2 for selective reduction of α,β-unsaturated carbonyl compounds in aqueous medium
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A facile strategy for the convenient reduction of α,β- unsaturated carbonyl compounds and conjugated alkynes has been accomplished by Mg-ZnCl2 system in aqueous medium. Georg Thieme Verlag Stuttgart.
- Saikia, Anil,Barthakur, Madan Gopal,Boruah, Romesh Chandra
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p. 523 - 525
(2007/10/03)
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- Enantioselective biotransformation of α,α-disubstituted dinitriles to the corresponding 2-cyanoacetamides using Rhodococcus sp. CGMCC 0497
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A new application of nitrile-converting enzymes in the synthesis of optically active α,α-disubstituted-α-cyanoacetamides from α,α-disubstituted-malononitriles with whole cells of Rhodococcus sp. CGMCC 0497 is described. The products were obtained with enantiomeric excesses of up to >99%, and yields of up to 53%. They are very useful chiral intermediates especially for the synthesis of chiral α,α-disubstituted amino acids but have never been synthesized directly by chemical or enzymatic methods.
- Wu, Zhong-Liu,Li, Zu-Yi
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p. 2133 - 2142
(2007/10/03)
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- Reduction of activated conjugated alkenes by the InCl3-NaBH 4 reagent system
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A combination of a catalytic amount of indium (III) chloride and sodium borohydride in acetonitrile reduces selectively the carbon-carbon double bonds in conjugated alkenes such as α,α-dicyano olefins, α,β-unsaturated nitriles, cyanoesters, cyanophosphonate and dicarboxylic esters. However, reduction of chalcones is little different. They are reduced to a mixture of saturated ketones and alcohols if the reaction mixture is quenched with H2O, whereas quenching with MeOH leads to saturated alcohols only.
- Ranu, Brindaban C.,Samanta, Sampak
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p. 7901 - 7906
(2007/10/03)
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- Use of indium hydride (Cl2InH) for chemoselective reduction of the carbon-carbon double bond in conjugated alkenes
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Indium hydride (Cl2InH) generated in situ from a combination of a catalytic amount of indium(III) chloride and sodium borohydride selectively reduces the carbon-carbon double bond in conjugated alkenes such as α,α-dicyano olefins, α,β-unsaturated nitriles, cyano esters, cyanophosphonate, diesters and ketones.
- Ranu, Brindaban C.,Samanta, Sampak
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p. 7405 - 7407
(2007/10/03)
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- Indium metal as a reducing agent. Selective reduction of the carbon-carbon double bond in highly activated conjugated alkenes
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(Equation presented) Indium metal in aqueous ethanolic ammonium chloride reduces the C=C bond in highly activated conjugated alkenes such as α,α-dicyano olefins, β-arylenones, and enone esters.
- Ranu, Brindaban C.,Dutta, Jyotirmoy,Guchhait, Sankar K.
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p. 2603 - 2605
(2007/10/03)
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- A detailed investigation into the oxidation mechanism in Hantzsch 1,4-dihydropyridines by ethyl a-cyanocinnamates and benzylidenemalononitriles
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A mechanism for the oxidation of Hantzsch 1,4-dihydropyridine (HEH) by substituted ethyl a-cyanocinnamates (1) and benzylidenemalononitriles (2) has been critically investigated. Replacement of HEH by HEH-4,4-d2 and HEH-N-d gave the observed kinetic isotope effects (KIE) of 5.3-6.0 and 1.2-1.3 for the reactions with 1 and 2, respectively, which suggests C4-H bond dissociation is involved in the rate-limiting step and that the N-H bond dissociation is a non-rate-limiting step. The positive ρ values of 1.78 and 1.67 for the reactions of HEH with 1 and 2, respectively, clearly demonstrate the electrophilic nature of the substrates in the transition state (TS) and so indicate that the hydrogen lost from HEH must be a hydride-like species. Correlation analyses on the kinetics, KIE's and activation parameters showed excellent linear dependence on the electronic properties of remote substituents and added further credence to the proposed one-step hydride transfer mechanism. Detailed investigation of the activation parameters not only confirmed the direct HT- mechanism, but also revealed experimentally, for the first time, an entropy-controlled compact TS for the HEH-modeled NAD(P)H oxidations.
- Zhu, Xiao-Qing,Zou, Hong-Ling,Yuan, Ping-Wei,Cao, Lei,Cheng, Jin-Pei
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p. 1857 - 1861
(2007/10/03)
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- Use of reductive properties of iodotrichlorosilane II: Chemoselective reduction of α,β-unsaturated ketones and nitriles
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A new synthetic procedure for the selective reduction of α,β-unsaturated ketones and nitriles, using iodotrichlorosilane (ITCS generated in situ from SiCl4-NaI) under mild conditions to produce the corresponding saturated ketone and nitrile compounds in quantitative yields, is described.
- Elmorsy, Saad S.,El-Ahl, Abdel-Aziz S.,Soliman, Hanan,Amer, Fathy A.
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p. 2297 - 2298
(2007/10/03)
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- Photochemical carbon-silicon bond forming reaction on electron-deficient alkenes by disilanes and polysilanes via photoinduced electron transfer
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The phenanthrene-sensitized photoreaction of electron-deficient alkenes with disilanes in acetonitrile gave silylated alkanes in high yields.The photosilylation occurred in a highly regioselective manner at the position β to the electron-withdrawing group
- Mizuno, Kazuhiko,Nakanishi, Kazuhisa,Chosa, Jun-ichi,Otsuji, Yoshio
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- PHOTOSILYLATION OF ELECTRON-DEFICIENT ALKENES BY USE OF DISILANES VIA PHOTOINDUCED ELECTRON-TRANSFER
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The photosilylation on electron-deficient alkenes such as 1-aryl-2,2-dicyanoethenes occurred regioselectively at the β-position to the electron-withdrawing groups upon irradiation with disilanes and trisilane.
- Mizuno, Kazuhiko,Nakanishi, Kazuhisa,Chosa, Jun-ichi,Nguyen, Tien,Otsuji, Yoshio
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p. 3689 - 3692
(2007/10/02)
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- REDUCTION SELECTIVE PAR LE BOROHYDRURE DE SODIUM D'UN GROUPE ESTER OU NITRILE DANS LES EPOXYDES GEM DISUBSTITUES PAR DEUX GROUPES ATTRACTEURS D'ELECTRONS.
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Sodium borohydride reduced the ester group of the epoxides 1 or one cyano group of 2 selectively within 5 minutes to give new hydroxy - or amino - functionalized epoxides.This unusual reduction of a cyano group has been extended to other α,α-dicyano derivatives.
- Mauger, J.,Robert, A.
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p. 2493 - 2502
(2007/10/02)
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- THE REACTIONS OF BENZYLIDENEMALONONITRILES AND β-NITROSTYRENES WITH O-PHENYLENEDIAMINE INCLUDING THE NEW ORGANIC REDOX REACTIONS BETWEEN THE OLEFINS AND 2-PHENYLBENZIMIDAZOLINES
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The reactions of benzylidenemalononitriles and β-nirtostyrenes with o-phenylenediamine in ethanol at boiling temperature gave the reduced products of the olefins.The reactions were rationalised on the basis of the role of 2-phenylbenzimidazolines as a hydrogen donor.
- Itoh, Kazuyoshi,Ishida, Hideaki,Chikashita, Hidenori
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p. 1117 - 1118
(2007/10/02)
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