- Successive oxidation-condensation reactions using a multifunctional gold-supported nanocomposite (Au/MgCe-HDO)
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The application of gold-supported nanocomposites is useful in clinical diagnostics because of their ability to provide bio-compatible and sensitive detection systems. A gold-supported magnesium hydroxide and cerium oxide nanocomposite framework (Au/MgCe-HDO) was synthesized and characterized via XRD, XPS, SEM, DLS, TEM, and TGA techniques. The nanocomposite was used as a selective catalyst for the aerobic oxidation of alcohols under mild reaction conditions followed by successive condensation reactions, like Knoevenagel and Claisen-Schmidt condensation. Substituted benzyl alcohols were converted into the corresponding carbonyl compounds in the presence of the Au/MgCe-HDO nanocomposite with O2 gas and toluene as a solvent. We observed that, upon the addition of malononitrile/ethyl cyanoacetate/acetophenone to the catalyst in the aerobic oxidation reaction, the reaction proceeds to produce the corresponding desired condensation product with up to 95% yield.
- Chandra, Ramesh,Kumar, Loveneesh,Kumar, Rupesh,Sehrawat, Hitesh,Tomar, Ravi,Verma, Nishant
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p. 3472 - 3481
(2022/02/21)
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- A useful method for the conversion of olefins to nitro olefins
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Triflyl nitrate is easily generated from tetra-n-butylammonium nitrate in CH2Cl2 solution and serves as an effective nitrating agent for a wide range of unsaturated substrates to form nitro olefins.
- Reddy, G. Sudhakar,Corey
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supporting information
p. 3399 - 3402
(2021/05/10)
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- Synthesis of Indoles by Reductive Cyclization of Nitro Compounds Using Formate Esters as CO Surrogates
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Alkyl and aryl formate esters were evaluated as CO sources in the Pd- and Pd/Ru-catalyzed reductive cyclization of 2-nitrostyrenes to give indoles. Whereas the use of alkyl formates requires the presence of a ruthenium catalyst such as Ru3(CO)12, the reaction with phenyl formate can be performed by using a Pd/phenanthroline complex alone. Phenyl formate was found to be the most effective CO source and the desired products were obtained in excellent yields, often higher than those previously reported using pressurized CO. The reaction tolerates many functional groups, including sensitive ones like a free aldehydic group or a pendant pyrrole. Detailed experiments and kinetic studies allow to conclude that the activation of phenyl formate is base-catalyzed and that the metal doesn't play a role in the decarbonylation step. The reactions can be performed in a single thick-walled glass tube with as little as 0.2 mol-% palladium catalyst and even on a 2 g scale. The same protocol can be extended to other nitro compounds, affording different heterocycles.
- Ahmed Fouad, Manar,Ferretti, Francesco,Formenti, Dario,Milani, Fabio,Ragaini, Fabio
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supporting information
p. 4876 - 4894
(2021/09/20)
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- N2H4-H2O Enabled Umpolung Cyclization of o-Nitro Chalcones for the Construction of Quinoline N-Oxides
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Umpolung is a unique strategy which converts the property of an atom into the opposite one. An efficient and general method for the construction of quinoline N-oxides via umpolung of carbonyl groups was developed from ortho-nitro chalcones and hydrazine i
- Zhang, Guan,Yang, Kai,Wang, Shihui,Feng, Qiang,Song, Qiuling
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supporting information
p. 595 - 600
(2021/02/03)
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- Promising Non-cytotoxic Monosubstituted Chalcones to Target Monoamine Oxidase-B
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A library of monosubstituted chalcones (1-17) bearing electron-donating and electron-withdrawing groups on both aromatic rings were selected. The cell viability on human tumor cell lines was evaluated first. The compounds unable to induce detectable cytotoxicity (1, 13, and 14) were tested using the monoamine oxidase (MAO) activity assay. Interestingly, they inhibit MAO-B, acting as competitive inhibitors, with 13 and 14 showing the best profiles. In particular, 13 exhibited a potency higher than that of safinamide, taken as a reference. Docking studies and crystallographic analysis showed that in human MAO-B 13 binds with the halogen-substituted aromatic ring in the entrance cavity, similar to safinamide, whereas 14 is accommodated in the opposite way. The main conclusion of this cell biology, biochemistry, and structural study is to highlights 13 as a chalcone derivative that is worth consideration for the development of novel MAO-B-selective inhibitors for the treatment of neurodegenerative diseases.
- Iacovino, Luca G.,Pinzi, Luca,Facchetti, Giorgio,Bortolini, Beatrice,Christodoulou, Michael S.,Binda, Claudia,Rastelli, Giulio,Rimoldi, Isabella,Passarella, Daniele,Di Paolo, Maria Luisa,Dalla Via, Lisa
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supporting information
p. 1151 - 1158
(2021/06/30)
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- Visible-light driven synthesis of polycyclic benzo[: D] [1,3]oxazocine from 2-aminochalcone
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Herein, we report a tandem cycloisomerization/nucleophilic addition/cyclization of 2-amino chalcone with bifunctional nucleophiles driven by visible light. This cascade process is realized by the irradiation of a blue LED at room temperature, which provides a concise route to structurally diverse benzo[d][1,3]oxazocine scaffolds. Mechanistic studies show that the reaction is initiated with the E to Z isomerization of a C-C double bond upon the irradiation of visible light, followed by cyclization/rearomatization to generate a transient quinolinium intermediate, which is trapped by the nucleophile and cyclized to produce the polycyclic benzo[d][1,3]oxazocine.
- Chen, Junhan,Gao, Yu-Qi,He, Yu-Peng,Hou, Yi,Li, Ruoxin,Xie, Weiqing,Zhang, Sheng-Yong,Zhu, Liming
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supporting information
p. 6739 - 6742
(2020/07/13)
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- Continuous Flow Synthesis of Quinolines via a Scalable Tandem Photoisomerization-Cyclization Process
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A continuous photochemical process is presented that renders a series of quinoline products via an alkene isomerization and cyclocondensation cascade. It is demonstrated that a high-power LED lamp generates the desired targets with higher productivity and efficiency than a medium-pressure Hg-lamp. The scope of this tandem process is established and allows for the generation of various substituted quinolines in high yields and with throughputs of greater than one gram per hour. Finally, this effective flow process is coupled with a telescoped hydrogenation reaction to render a series of tetrahydroquinolines including the antimalarial natural product galipinine.
- Di Filippo, Mara,Baumann, Marcus
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p. 6199 - 6211
(2020/08/26)
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- Superbase-Mediated Indirect Friedl?nder Reaction: A Transition Metal-Free Oxidative Annulation toward Functionalized Quinolines
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A superbase mediated indirect Friedl?nder reaction towards functionalized quinolines has been realized. The reaction was performed with o-aminobenzyl alcohol and ketones having an active methylene moiety in the presence of KOH and in DMSO. The reaction proceeds predominantly via initial formation of an imine intermediate and subsequent oxidation of the benzyl alcohol functionality and condensation to afford substituted quinolines. We could also demonstrate that a minor fraction of the reaction proceeds via a chalcone intermediate. The transition metal-free oxidative annulation was found to be general affording 2-substituted, 2,3-disubstituted/fused or multi-substituted quinolines. The reaction was extended towards the functionalization of natural products and the applicability of the reaction for gram-scale synthesis of quinolines was also demonstrated.
- Rahul,Nitha,Omanakuttan, Vishnu K.,Babu, Sheba Ann,Sasikumar,Praveen, Vakayil K.,Hopf, Henning,John, Jubi
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p. 3081 - 3089
(2020/05/08)
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- Antiproliferative effects of chalcones on T cell acute lymphoblastic leukemia-derived cells: Role of PKCβ
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In this study, a series of 20 chalcone derivatives was synthesized, and their antiproliferative activity was tested against the human T cell acute lymphoblastic leukemia-derived cell line, CCRF-CEM. On the basis of the structural features of the most active compounds, a new library of chalcone derivatives, according to the structure–activity relationship design, was synthesized, and their antiproliferative activity was tested against the same cancer cell line. Furthermore, four of these derivatives (compounds 3, 4, 8, 28), based on lower IC50 values (between 6.1 and 8.9 μM), were selected for further investigation regarding the modulation of the protein expression of RACK1 (receptor for activated C kinase), protein kinase C (PKC)α and PKCβ, and their action on the cell cycle level. The cell cycle analysis indicated a block in the G0/G1 phase for all four compounds, with a statistically significant decrease in the percentage of cells in the S phase, with no indication of apoptosis (sub-G0/G1 phase). Compounds 4 and 8 showed a statistically significant reduction in the expression of PKCα and an increase in PKCβ, which together with the demonstration of an antiproliferative role of PKCβ, as assessed by treating cells with a selective PKCβ activator, indicated that the observed antiproliferative effect is likely to be mediated through PKCβ induction.
- Corsini, Emanuela,Facchetti, Giorgio,Esposito, Sara,Maddalon, Ambra,Rimoldi, Isabella,Christodoulou, Michael S.
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- Deciphering a Reaction Network for the Switchable Production of Tetrahydroquinoline or Quinoline with MOF-Supported Pd Tandem Catalysts
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A mechanistic study of heterogeneous tandem catalytic systems is crucial for understanding and improving catalyst activity and selectivity but remains challenging. Here, we demonstrate that a thorough mechanistic study of a multistep reaction can guide us to the controllable selective synthesis of phenyltetrahydroquinoline or phenylquinoline with easily accessible precursors. The one-pot production can be achieved, catalyzed by a well-defined, bifunctional metal-organic framework-supported Pd nanoparticles, with only water as the side product. Our mechanistic study identifies six transient intermediates and ten transformation steps from the operando magic angle spinning nuclear magnetic resonance study under 27.6 bar H2. In particular, reactive intermediate 2-phenyl-3,4-dihydroquinoline cannot be observed with conventional chromatographic techniques but is found to reach the maximal concentration of 0.11 mol L-1 under the operando condition. The most probable reaction network is further deduced based on the kinetic information of reaction species, obtained from both operando and ex situ reaction studies. This deep understanding of the complex reaction network enables the kinetic control of the conversions of key intermediate, 2-phenyl-3,4-dihydroquinoline, with the addition of a homogeneous co-catalyst, allowing the selective production of tetrahydroquinoline or quinoline on demand. The demonstrated methods in this work open up new avenues toward efficient modulation of reactions with a complex network to achieve desired selectivities.
- Bao, Zongbi,Chen, Jingwen,Huang, Wenyu,Kobayashi, Takeshi,Nie, Renfeng,Qi, Long,Qi, Zhiyuan,Ren, Qilong,Sun, Qi,Yang, Qiwei,Zhang, Biying,Zhang, Zhiguo
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p. 5707 - 5714
(2020/09/02)
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- tert-Butoxide-Mediated Synthesis of 3,4′-Biquinolines from 2-Aminochalcones
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A novel protocol to synthesize 3,4’-biquinolines from 2-aminochalcones in the presence of a stoichiometric amount of sodium tert-butoxide as the nucleophilic promotor was developed. Conjugate addition of tert-butoxide to 2-aminochalcones provided the corresponding enolates, which underwent Michael addition to another molecule of 2-aminochalcone to afford a dimeric species of 2-aminochalcones. Subsequent cyclization between the amino and carbonyl groups followed by aromatization provides 3,4’-biquinoline products. Various 2-aminochalcones were submitted to this protocol and the desired 3,4’-biquinoline products were obtained in good to high yields in a short reaction time. (Figure presented.).
- Jeon, Jiye,Lee, So Young,Cheon, Cheol-Hong
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supporting information
p. 2360 - 2364
(2019/04/25)
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- Visible-Light Induction/Br?nsted Acid Catalysis in Relay for the Enantioselective Synthesis of Tetrahydroquinolines
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An efficient method merging Br?nsted acid catalysis with visible-light induction for the highly enantioselective synthesis of tetrahydroquinolines has been developed. This mild process directly transforms 2-aminoenones into 2-substituted tetrahydroquinolines with excellent enantioselectivities through a relay visible-light-induced cyclization/chiral phosphoric acid-catalyzed transfer hydrogenation reaction.
- Xiong, Wenhui,Li, Shan,Fu, Bo,Wang, Jinping,Wang, Qiu-An,Yang, Wen
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supporting information
p. 4173 - 4176
(2019/06/07)
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- Iodine mediated pyrazolo-quinoline derivatives as potent anti-proliferative agents
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A novel series of substituted pyrazolo-quinoline derivatives 7pa–7qg were synthesized efficiently by using molecular iodine in DMSO and further characterized based on 1H NMR, 13C NMR, IR and HRMS spectral studies. All the synthesized
- Kasaboina, Suresh,Ramineni, Venkatesh,Banu, Saleha,Bandi, Yadagiri,Nagarapu, Lingaiah,Dumala, Naresh,Grover, Paramjit
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supporting information
p. 664 - 667
(2018/02/12)
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- Synthesis of 2-Substituted Quinolines from 2-Aminostyryl Ketones Using Iodide as a Catalyst
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A new protocol for the synthesis of 2-substituted quinolines from 2-aminostyryl ketones has been developed using iodide as a nucleophilic catalyst. Conjugate addition of iodide to 2-aminostyryl ketones yielded the corresponding β-iodoketones, which could have a conformation where the amino and carbonyl groups are proximal through free rotation about the Cα-Cβ single bond. Subsequent condensation between the amino and carbonyl groups followed by elimination of hydrogen iodide provided the corresponding quinolines, with regeneration of the iodide catalyst.
- Lee, So Young,Jeon, Jiye,Cheon, Cheol-Hong
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p. 5177 - 5186
(2018/05/15)
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- Three-Component Synthesis of a Library of m-Terphenyl Derivatives with Embedded β-Aminoester Moieties
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The three-component reaction between alkyl- or arylamines, β-ketoesters and chalcones in refluxing ethanol containing a catalytic amount of Ce(IV) ammonium nitrate allowed the construction of a large library of highly substituted dihydro-m-terphenyl derivatives containing β-alkylamino- or β-arylamino ester moieties. This process generates three new bonds and one ring and proceeds in high atom economy, having two molecules of water as the only side product. Another domino process, in which the original MCR was telescoped with a subsequent aza Michael/retro-aza Michael sequence, allowed the one-pot preparation of a library of compounds with a N-unsubstituted β-aminoester fragment. Finally, to extend the structural diversity of these libraries, we also examined the aromatization of the central ring of our compounds in the presence of dichlorodicyanoquinone. This reaction sequence did not affect the integrity of a stereogenic center belonging to the amino component.
- Rocchi, Damiano,González, Juan F.,Gómez-Carpintero, Jorge,González-Ruiz, Víctor,Martín, M. Antonia,Sridharan, Vellaisamy,Menéndez, J. Carlos
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p. 722 - 731
(2018/10/20)
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- On-Water Synthesis of 2-Substituted Quinolines from 2-Aminochalcones Using Benzylamine as the Nucleophilic Catalyst
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On-water synthesis of 2-substituted quinolines from 2-aminochalcone derivatives was developed using benzylamine as the nucleophilic catalyst. Various 2-aminochalcones could be applied to this protocol, and the desired 2-substituted quinoline products were isolated in excellent yields by simple filtration. Furthermore, we elucidated the role of benzylamine in this transformation and provided the detailed reaction mechanism. This protocol has several additional advantages, such as simple operation, broad substrate scope, good functional group tolerance, easy product isolation, recycling of the catalyst, and gram-scale synthesis.
- Lee, So Young,Cheon, Cheol-Hong
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p. 13036 - 13044
(2018/11/20)
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- Asymmetric synthesis of CF3-containing tetrahydroquinoline: Via a thiourea-catalyzed cascade reaction
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An organocatalytic asymmetric method for the synthesis of 2-CF3 tetrahydroquinoline has been achieved. The cascade reaction of 2-aminochalcones with β-CF3 nitroalkenes afforded the products bearing three contiguous stereogenic centers in good yields with excellent diastereoselectivities and enantioselectivities.
- Zhu, Yuanyuan,Li, Boyu,Wang, Cui,Dong, Zhenghao,Zhong, Xiaoling,Wang, Kairong,Yan, Wenjin,Wang, Rui
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supporting information
p. 4544 - 4547
(2017/07/10)
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- Synthesis and evaluation of modified chalcone based p53 stabilizing agents
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Tumor suppressor protein p53 induces cell cycle arrest and apoptotic cell death in response to various cellular stresses thereby preventing cancer development. Activation and stabilization of p53 through small organic molecules is, therefore, an attractive approach for the treatment of cancers retaining wild-type p53. In this context, a series of nineteen chalcones with various substitution patterns of functional groups including chloro, fluoro, methoxy, nitro, benzyloxy, 4-methyl benzyloxy was prepared using Claisen-Schmidt condensation. The compounds were characterized using NMR, HRMS, IR and melting points. Evaluation of synthesized compounds against human colorectal (HCT116) and breast (CAL-51) cancer cell lines revealed potent antiproliferative activities. Nine compounds displayed GI50 values in the low micromolar to submicromolar range; for example (E)-1-phenyl-3-(3,4,5-trimethoxyphenyl)prop-2-en-1-one (SSE14108) showed GI50 of 0.473 ± 0.043 μM against HCT116 cells. Further analysis of these compounds revealed that (E)-3-(4-chlorophenyl)-1-phenylprop-2-en-1-one (SSE14105) and (E)-3-(4-methoxyphenyl)-1-phenylprop-2-en-1-one (SSE14106) caused rapid (4 and 8-h post-treatment) accumulation of p53 in HCT116 cells similar to its induction by positive control, Nutlin-3. Such activities were absent in 3-(4-methoxyphenyl)propiophenone (SSE14106H2) demonstrating the importance of conjugated ketone for antiproliferative and p53 stabilizing activity of the chalcones. We further evaluated p53 levels in the presence of cycloheximide (CHX) and the results showed that the p53 stabilization was regulated at post-translational level through blockage of its degradation. These chalcones can, therefore, act as fragment leads for further structure optimization to obtain more potent p53 stabilizing agents with enhanced anti-proliferative activities.
- Iftikhar, Sunniya,Khan, Sardraz,Bilal, Aishah,Manzoor, Safia,Abdullah, Muhammad,Emwas, Abdel-Hamid,Sioud, Salim,Gao, Xin,Chotana, Ghayoor Abbas,Faisal, Amir,Saleem, Rahman Shah Zaib
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supporting information
p. 4101 - 4106
(2017/08/22)
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- One-Pot Synthesis of Functionalized Carbazoles via a CAN-Catalyzed Multicomponent Process Comprising a C-H Activation Step
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The microwave-promoted three-component reaction between o-nitrochalcones, primary amines and β-dicarbonyl compounds in the presence of Ce(IV) ammonium nitrate constitutes the first example of a multicomponent carbazole synthesis. This reaction furnishes highly substituted and functionalized carbazole derivatives via a double annulation process that generates two C-C and two C-N bonds, with water as the only side product. Mechanistically, this transformation has some unusual features that include an intramolecular coupled hydrogenation-dehydrogenation process, the functionalization of a C-H group by direct attack onto a nitrogen function and a CAN-catalyzed reduction via hydride transfer from ethanol. The mechanisms of these reactions were studied with the aid of computational techniques.
- González, Juan F.,Rocchi, Damiano,Tejero, Tomás,Merino, Pedro,Menéndez, J. Carlos
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supporting information
p. 7492 - 7502
(2017/07/26)
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- Synthesis, spectroscopic and X-ray structural characterization, quantum chemical studies and investigation of gama-irradiated effects of the novel hydrazone compound: [(E)-3-(2-nitrophenyl)-(E)-1-(2-phenylhydrazono)]-1-phenylallylidene
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The novel hydrazone compound, [(E)-3-(2-nitrophenyl)-(E)-1-(2-phenylhydrazono)]-1-phenylallylidene (2), has been synthesized, characterized by FTIR, 1H NMR, 13C NMR techniques, elemental analysis, X-ray structure analysis and has bee
- Yakal?, Gül,?ak?c?, Abban,Eke, Canel,Cin, Günseli Turgut,Aygün, Muhittin
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p. 244 - 252
(2017/01/09)
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- Organocatalyzed aerobic oxidative Robinson-type annulation of 2-isocyanochalcones: expedient synthesis of phenanthridines
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A DBU-catalyzed aerobic oxidative Robinson annulation of 2-isocyanochalcones with active methylene ketones was developed for the expedient synthesis of phenanthridines in high to excellent yields. This unprecedented multistep domino reaction represents a
- Hu, Zhongyan,Dong, Jinhuan,Men, Yang,Li, Yifei,Xu, Xianxiu
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supporting information
p. 1739 - 1742
(2017/02/10)
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- Blue-light-promoted carbon-carbon double bond isomerization and its application in the syntheses of quinolines
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A blue-light-promoted carbon-carbon double bond isomerization in the absence of any photoredox catalyst is reported. It provides rapid access to a series of quinolines in good to excellent yields under simple aerobic conditions. The protocol is direct, catalyst-free and operationally convenient.
- Chen, Xinzheng,Qiu, Shuxian,Wang, Sasa,Wang, Huifei,Zhai, Hongbin
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supporting information
p. 6349 - 6352
(2017/08/10)
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- Phosphorous Acid Promoted Hydration-Condensation of Aromatic Alkynes with Aldehydes Affording Chalcones in an Oil/Water Two-Phase System
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A simple and environmentally benign method was developed for the synthesis of chalcones in high to excellent yields by a phosphorous acid promoted alkyne-aldehyde hydration-condensation in an oil/water two-phase system. The method is the first efficient protocol for the preparation of chalcones that is mediated by a simple Bronsted acid in a two-phase system.
- Zhou, Yongbo,Li, Zhongwen,Yang, Xiao,Chen, Xiulin,Li, Mei,Chen, Tieqiao,Yin, Shuang-Feng
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p. 231 - 237
(2016/01/12)
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- Cross-Cycloaddition of Two Different Isocyanides: Chemoselective Heterodimerization and [3+2]-Cyclization of 1,4-Diazabutatriene
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A new cross-cycloaddition reaction between a wide range of isocyanides and 2-isocyanochalcones (or analogues) was developed for the expeditious synthesis of pyrrolo[3,4-b]indoles under thermal conditions. On the basis of the experimental results and DFT c
- Hu, Zhongyan,Yuan, Haiyan,Men, Yang,Liu, Qun,Zhang, Jingping,Xu, Xianxiu
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supporting information
p. 7077 - 7080
(2016/07/06)
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- Carbon-carbon bond formation in acid deep eutectic solvent: Chalcones synthesis: Via Claisen-Schmidt reaction
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One of the most studied properties of novel organic solvents is represented by their use as media for many chemical reactions. In this field Ionic Liquids (ILs) and more recently Deep Eutectic Solvents (DESs) have been playing significant roles for their smart properties. DESs are increasing their relevance thanks to their low toxicity, and because of their simple and cheap preparation that can be carried out by simply mixing two compounds. In this work we present the studies of the use of an acid DES obtained from 3-(cyclohexyldimethylammonio)propane-1-sulfonate and (1S)-(+)-10-camphorsulfonic acid (SB3-Cy/CSA) as reaction media and catalyst for carbon-carbon bond formation reaction via Claisen-Schmidt condensation. This powerful and widely used aldol condensation was performed without the use of any catalysts that are usually needed in this reaction, because of the presence of acid CSA in the DES components. We synthesised fourteen substituted chalcones from benzaldehydes and substituted benzaldehydes in combination with acetophenone and substituted acetophenones as probe reactions. The advantages of the use of this DES in this relevant reaction are represented by: the green properties of the media and its low toxicity; the absence of harmful acids to catalyse the aldol condensation because of the camphorsulfonic acid composing the DES mixture; the recycling and the re-use of the DES in subsequent reaction cycles; the mild conditions and the excellent conversions and yields observed.
- Tiecco, Matteo,Germani, Raimondo,Cardellini, Fabio
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p. 43740 - 43747
(2016/05/24)
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- Substituent-Controlled Chemoselective Cleavage of C = C or Csp2 - C(CO) Bond in α,β-Unsaturated Carbonyl Compounds with H-Phosphonates Leading to β-Ketophosphonates
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An unprecedented substituent-controlled chemoselective cleavage of C = C double bond or C(sp2)-C(CO) bond along with aerobic phosphorylation of α,β-unsaturated carbonyl compounds with H-phosphonates through a radical process has been disclosed. The current strategy provides an access to β-ketophosphonates under mild conditions with a wide substrate scope.
- Zhou, Yao,Rao, Changqing,Mai, Shaoyu,Song, Qiuling
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p. 2027 - 2034
(2016/03/15)
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- Iron-facilitated oxidative radical decarboxylative cross-coupling between α-oxocarboxylic acids and acrylic acids: An approach to α,β-unsaturated carbonyls
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The first Fe-facilitated decarboxylative cross-coupling reaction between α-oxocarboxylic acids and acrylic acids in aqueous solution has been developed. This transformation is characterized by its wide substrate scope and good functional group compatibility utilizing inexpensive and easily accessible reagents, thus providing an efficient and expeditious approach to an important class of α,β-unsaturated carbonyls frequently found in bioactive compounds. The synthetic potential of the coupled products is also demonstrated in subsequent functionalization reactions. Preliminary mechanism studies suggest that a free radical pathway is involved in this process: the generation of an acyl radical from α-oxocarboxylic acid via the excision of carbon dioxide followed by the addition of an acyl radical to the α-position of the double bond in acrylic acid then delivers the α,β-unsaturated carbonyl adduct through the extrusion of another carbon dioxide.
- Jiang, Qing,Jia, Jing,Xu, Bin,Zhao, An,Guo, Can-Cheng
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p. 3586 - 3596
(2015/04/22)
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- N-bromosuccinimide/cerium ammonium nitrate: An efficient reagent for stereo-controlled deamination of ketoaziridines
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An efficient and novel method for the deamination of trans-1-alkyl (H or benzoyl)-2-aroyl aziridines in a completely stereo-controlled reaction in the presence of N-bromosuccinimide/cerium (IV) ammonium nitrate is described. In comparison with the previous reported work, this reaction reveals a substituent-reactivity relationship and important role for the substituent on C1 and C2 in determining whether deamination or oxidation reaction takes place.
- Samimi, Heshmat Allah,Salehi, Elham,Dadvar, Farkhondeh
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p. 731 - 733
(2015/03/03)
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- Synthesis and xanthine oxidase inhibitory activity of 5,6-dihydropyrazolo/pyrazolo[1,5-c]quinazoline derivatives
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Some 5,6-dihydropyrazolo/pyrazolo[1,5-c]quinazoline derivatives were rationally designed, synthesized and evaluated for in vitro xanthine oxidase inhibitory activity for the first time. Some notions about structure activity relationships are presented. Th
- Kumar, Deependra,Kaur, Gagandeep,Negi, Arvind,Kumar, Sanjeev,Singh, Sandeep,Kumar, Raj
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- Montmorillonite clay-promoted, solvent-free cross-aldol condensations under focused microwave irradiation
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An environmentally benign, clean and general protocol was developed for the synthesis of aryl and heteroaryl trans-chalcones. This method involved solvent-free reaction conditions under microwave irradiation in the presence of a clay-based catalyst, and afforded the target compounds in good yields and short reaction times. Furthermore, the same conditions allowed the synthesis of symmetrical, diarylmethylene-a,a-unsaturated ketones from aromatic aldehydes and ketones.
- Rocchi, Damiano,Gonzalez, Juan F.,Menendez, J. Carlos
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supporting information
p. 7317 - 7326
(2014/07/08)
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- One pot synthesis of pyrrolo[3,4-c]quinolinone/pyrrolo[3,4-c]quinoline derivatives from 2-aminoarylacrylates/2-aminochalcones and tosylmethyl isocyanide (TosMIC)
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An efficient and practical synthetic approach to access to 2H-pyrrolo[3,4-c]quinolin-4(5H)-one/2H-pyrrolo[3,4-c]quinoline derivatives by the reaction of 2-aminoarylacrylates/2-aminochalcones and tosylmethyl isocyanide (TosMIC) via a one pot van Leusen rea
- Lu, Xin-Mou,Li, Jian,Cai, Zhong-Jian,Wang, Rong,Wang, Shun-Yi,Ji, Shun-Jun
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p. 9471 - 9477
(2015/02/19)
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- Iodine-mediated intramolecular amination of ketones: The synthesis of 2-acylindoles and 2-acylindolines by tuning N-protecting groups
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A general method for constructing both 2-acylindoles and 2-acylindolines via I2-mediated intramolecular C-N bond formation is presented, and the selective formation of either 2-acylindoles or 2-acylindolines just depends on the nitrogen protecting groups used in the same substrate skeletons. The Royal Society of Chemistry.
- Gao, Wen-Chao,Jiang, Shan,Wang, Ruo-Lin,Zhang, Chi
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supporting information
p. 4890 - 4892
(2013/07/05)
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- Organocatalytic enantioselective cascade aza-michael/michael addition for the synthesis of highly functionalized tetrahydroquinolines and tetrahydrochromanoquinolines
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An efficient organocatalytic highly asymmetric cascade aza-Michael/Michael addition reaction for the synthesis of tetrahydroquinolines and tetrahydrochromanoquinolines has been developed. This cascade reaction proceeds well at low catalyst loading with a broad substrate scope, furnishing the desired products in excellent yields with excellent diastereoselectivities and enantioselectivities (up to >99:1 dr, 99% ee) under mild conditions. Importantly, it is the first catalytic asymmetric method for tetrahydrochromanoquinolines. This protocol provides a straightforward entry to highly functionalized chiral tetrahydroquinoline and tetrahydrochromanoquinoline derivatives from simple starting materials. Copyright
- Yang, Wen,He, Hai-Xiao,Gao, Yu,Du, Da-Ming
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supporting information
p. 3670 - 3678
(2014/01/06)
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- NUCLEAR RECEPTOR MODULATORS AND THEIR USE FOR THE TREATMENT AND PREVENTION OF CANCER
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Disclosed are compounds which are nuclear receptor modulators that can act as antagonists to the androgen receptor, for example, a compound of Formula I: wherein R1 to R5 and X1 to X5 are as described herein, as well as pharmaceutically acceptable salts, solvates, and stereoisomers thereof. Pharmaceutical compositions comprising such compounds, as well as methods of use, and treatment for cancers, including prostate cancers, other nuclear receptor mediated cancers, and other conditions, are also disclosed.
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Page/Page column 23
(2013/02/28)
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- Pd-catalyzed cross-coupling of aryl carboxylic acids with propiophenones through a combination of decarboxylation and dehydrogenation
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A palladium-catalyzed cross-coupling reaction of aryl carboxylic acids with saturated propiophenones through a combination of decarboxylation and dehydrogenation to form Heck-type products was reported. In a glove box, a 25 mL tube equipped with a stir bar was charged with Pd(OAc)2, PCy3, propiophenone, 2-nitrobenzoic acid, Ag2CO3 and nBu4NOAc HOAc. Then, the mixture was heated under nitrogen at 90°C in DMF for 24 h. After cooling down, the crude reaction mixture was analyzed by GC with n-dodecane as an internal standard to obtain 3a in 75% GC yield. Relatively weak bases, such as carboxylate salts, facilitated this reaction and the effect of the bases was a function of their solubility, while strong bases, such as K3PO4 and K2CO3 shut down the reaction completely. The simultaneous use of carboxylate salts and equimolar carboxylic acids significantly improved the yield of 3a, although the use of acetic acid alone was ineffective for the reaction.
- Zhou, Jun,Wu, Ge,Zhang, Min,Jie, Xiaoming,Su, Weiping
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supporting information; experimental part
p. 8032 - 8036
(2012/08/13)
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- Solvent-free selective cross-aldol condensation of ketones with aromatic aldehydes efficiently catalyzed by a reusable supported acidic ionic liquid
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A newly prepared catalyst consisting of acidic ionic liquid 1-(4-sulfonic acid) butylpyridinium hydrogen sulfate supported on silica was used to catalyze the cross-aldol condensation of ketones with aromatic aldehydes under solvent-free conditions. The highly active and selective catalyst gave good to excellent yields of the desired cross-aldol products without the occurrence of any self-condensation reactions. Reaction times were short, the procedure and work-up were simple, and no volatile or hazardous organic solvents were necessary. Moreover, the catalyst could be reused at least four times with only a slight reduction in activity.
- Davoodnia, Abolghasem,Yassaghi, Ghazaleh
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p. 1950 - 1957
(2013/02/25)
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- Novel chalcone derivatives as potent Nrf2 activators in mice and human lung epithelial cells
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Nrf2-mediated activation of antioxidant response element is a central part of molecular mechanisms governing the protective function of phase II detoxification and antioxidant enzymes against carcinogenesis, oxidative stress, and inflammation. Nrf2 is sequestered in the cytoplasm by its repressor, Keap1. We have designed and synthesized novel chalcone derivatives as Nrf2 activators. The potency of these compounds was measured by the expression of Nrf2 dependent antioxidant genes GCLM, NQO1, and HO1 in human lung epithelial cells, while the cytotoxicity was analyzed using MTT assay. In vivo potency of identified lead compounds to activate Nrf2 was evaluated using a mouse model. Our studies showed 2-trifluoromethyl-2′-methoxychalone (2b) to be a potent activator of Nrf2, both in vitro and in mice. Additional experiments showed that the activation of Nrf2 by this compound is independent of reactive oxygen species or redox changes. We have discussed a quantitative structure-activity relationship and proposed a possible mechanism of Nrf2 activation.
- Kumar, Vineet,Kumar, Sarvesh,Hassan, Mohammad,Wu, Hailong,Thimmulappa, Rajesh K.,Kumar, Amit,Sharma, Sunil K.,Parmar, Virinder S.,Biswal, Shyam,Malhotra, Sanjay V.
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experimental part
p. 4147 - 4159
(2011/08/03)
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- Highly enantioselective synthesis of polysubstituted tetrahydroquinolines via organocatalytic Michael/Aza-Henry tandem reactions
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Highly enantioselective chiral bifunctional thiourea catalyzed asymmetric tandem reactions for synthesis of substituted tetrahydroquinolines are described. Substituted tetrahydroquinolines were given in good yields (up to 98%), high enantioselectivities (
- Jia, Zhen-Xin,Luo, Yong-Chun,Xu, Peng-Fei
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supporting information; scheme or table
p. 832 - 835
(2011/04/27)
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- Hydrogenation of ortho-nitrochalcones over Pd/C as a simple access to 2-substituted 1, 2, 3, 4-tetrahydroquinolines
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The preparation of some 2-substituted-1, 2, 3, 4-tetrahydroquinoline has been achieved by the one-pot reductive intramolecular cyclization of ortho-nitrochalcones with gaseous hydrogen in the presence of a Pd/C catalyst and the best selectivity was observed using CH2Cl2 as solvent. The method is operationally simple and versatile since ortho-nitrocalchones are easily accessible by Claisen-Schmidt condensation of 2-nitrobenzaldehydes and enolizable ketones. Selected examples on structurally different substrates have been considered and a novel tetrahydroquinoline and a benzo[h]tetrahydroquinoline were prepared and characterised.
- Patti, Angela,Pedotti, Sonia
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experimental part
p. 5607 - 5611
(2010/09/18)
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- 'On water' synthesis of 2,4-diaryl-2,3-dihydro-1,5-benzothiazepines catalysed by sodium dodecyl sulfate (SDS)
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An efficient synthesis of 1,3-diaryl-2,3-dihydro-1,5-benzothiazepines has been developed by the reaction of various 1,3-diaryl-2-propenones with 2-aminothiophenol in water under neutral conditions catalysed by SDS. Excellent chemoselectivity was observed for substrates possessing halogen atoms or nitro/alkoxy/thioalkyl groups which did not undergo competitive aromatic nucleophilic substitution of the halogen atoms or the nitro group, reduction of the nitro or the α,β-unsaturated carbonyl group, or dealkylation of the alkoxy/thioalkoxy groups.
- Sharma, Gaurav,Kumar, Raj,Chakraborti, Asit K.
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p. 4269 - 4271
(2008/09/21)
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- Reductive coupling reactions of 2-nitrochalcones and their β-hydroxy-analogues: New syntheses of 2-arylquinoline and 2-aryl-4-hydroxyquinoline derivatives
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A one-pot synthesis of novel 2-arylquinolines and 2-aryl-4- hydroxyquinolines was developed from the intramolecular reductive coupling reactions of 2-nitrochalcones and 3-hydroxy-1-phenyl-3-(2-nitrophenyl)-2-propen- 1-ones. Depending on the reduction method and on the presence of electron donating substituents on the A ring of 2-nitrochalcones one can modulate the formation of 2-arylquinolines, their N-oxides, and of 2-aminochalcones. The reduction of 3-hydroxy-1-(2-hydroxyphenyl)-3-(2-nitrophenyl)-2-propen-1-ones with stannous chloride in hydrochloric acid gave 2′-aminoflavones and with ammonium formate and Pd/C yielded 2-(2-hydroxyaryl)-4-hydroxyquinolines. Springer-Verlag 2007.
- Barros, Ana I.R.N.A.,Dias, Andre F. R.,Silva, Artur M. S.
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p. 585 - 594
(2008/02/03)
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- Indium-mediated reductive cyclization of 2-nitrochalcones to quinolines
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The reductive cyclization of 2-nitrochalcones using indium in an aqueous alcohol solution containing ammonium chloride produced the corresponding quinolines in reasonable yields.{A figure is presented}.
- Han, Rongbi,Chen, Shen,Lee, Sun Jung,Qi, Fang,Wu, Xue,Kim, Byeong Hyo
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p. 1675 - 1684
(2007/10/03)
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- Ytterbium triflate promoted coupling reaction between aryl alkynes and aldehydes
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A simple and efficient solvent-free coupling reaction affording regioselectively trans-α,β-enones from aryl alkynes and aldehydes catalysed by Yb(OTf)3 hydrate is described.
- Curini, Massimo,Epifano, Francesco,Maltese, Federica,Rosati, Ornelio
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p. 552 - 554
(2007/10/03)
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- A novel one-pot synthesis of 2-arylquinolines through cascade reactions mediated by samarium reagents
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A novel one-pot synthesis of 2-arylquinolines 4 from onitrobenzaldehydes 1 and α-haloketones 2 through SmI3 and Sm (II) mediated cascade reactions is reported. The advantages of this new one-pot procedure are easily accessible substrates, simple and mild reaction conditions.
- Fan, Xuesen,Zhang, Yongmin
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p. 655 - 657
(2007/10/03)
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- Synthesis, characterization and in vitro antifungal evaluation of tetrahydropyrazolo[1,5-c]quinazolines
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The synthesis of a series of new pyrazolo[1,5-c]quinazolines starting from 2-nitrobenzaldehyde is described. The structures of the obtained compounds were established by NMR and X-ray diffraction. In contrast with other quinazoline derivatives, these comp
- Insuasty, Braulio,Torres, Harlem,Quiroga, Jairo,Abonia, Rodrigo,Nogueras, Manuel,Sanchez, Adolfo,Sortino, Maximiliano,Zacchino, Susana,Low, John
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p. 153 - 160
(2007/10/03)
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- In vitro antifungal evaluation and structure-activity relationships of a new series of chalcone derivatives and synthetic analogues, with inhibitory properties against polymers of the fungal cell wall
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Here we report the synthesis, in vitro antifungal evaluation and SAR study of 41 chalcones and analogues. In addition, all active structures were tested for their capacity of inhibiting Saccharomyces cerevisiae β(1,3)-glucan synthase and chitin synthase,
- Lopez, Silvia N.,Castelli, Maria V.,Zacchino, Susana A.,Dominguez, Jose N.,Lobo, Gricela,Charris-Charris, Jaime,Cortes, Juan C.G.,Ribas, Juan C.,Devia, Cristina,Rodriguez, Ana M.,Enriz, Ricardo D.
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p. 1999 - 2013
(2007/10/03)
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- Synthesis of 2-Acyl- and 2-Benzoylindoles
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2-Nitrobenzaldehydes (3a-c) on reaction with phosphoranes (4a and 4b), and triphenyl phosphine in refluxing diphenylether provide 2-acylindoles (6a-c) and 2-benzoylindoles (6d-f). Alternatively 2-nitrobenzaldehydes (3a-c) on reaction with phosphoranes (4a and 4b) give nitroketones (5a-f) which on refluxing with triphenyl phosphine in refluxing diphenyl ether furnish 2-acyl- and 2-benzoylindoles (6a-f).
- Mali, Raghao S.,Tilve, Santosh G.,Desai, Vidya G.
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p. 150 - 158
(2007/10/03)
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- Kinetics of Iodide Ion Induced Debromination of Chalcone Dibromides
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Iodide ion induced debromination of various chalcone dibromides in isopropanol-DMSO mixture (80:20, v/v) follows total second order kinetics, first order each in chalcone dibromide and iodide ion.All substituents, regadless of their electronic nature, facilitate the reaction.The isokinetic relationship holds good and β = 33 deg C.The effect of change of isopropanol content and replacement of isopropanol by methanol, ethanol and n-propanol on the rate of debromination has been studied and the data rationalised on the basis of varying hydrogen bonding abilities of the alcohols with the iodide ion.
- Raghavan, R. S.,Velayutham, K.,Rajendran, V.
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p. 466 - 469
(2007/10/02)
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