- Electrochemical esterification via oxidative coupling of aldehydes and alcohols
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An electrolytic method for the direct oxidative coupling of aldehydes with alcohols to produce esters is described. Our method involves anodic oxidation in presence of TBAF as supporting electrolyte in an undivided electrochemical cell equipped with graphite electrodes. This method successfully couples a wide range of alcohols to benzaldehydes with yields ranging from 70 to 90%. The protocol is easy to perform at a constant voltage conditions and offers a sustainable alternative over conventional methods.
- Smeyne, Dylan,Verboom, Katherine,Bryan, Maria,LoBue, James,Shaikh, Abid
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supporting information
(2021/03/26)
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- Photoinduced Cross-Coupling of Aryl Iodides with Alkenes
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A protocol for photoinduced cross-coupling of aryl iodides having polar π-functional groups or elongated π-conjugation with alkenes has been developed. The radical cascade mechanism involving generation of aryl radicals via C-I bond homolysis of photoexcited aryl iodides and their subsequent addition to alkenes is proposed. The method enables iodide-selective cross-coupling over other halogen leaving groups with functional group compatibility on both arene and alkene motifs.
- Liu, Yuliang,Li, Haoyu,Chiba, Shunsuke
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supporting information
p. 427 - 432
(2021/01/26)
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- Ultrafine Copper Oxide Particles Dispersed on Nitrogen-Doped Hollow Carbon Nanospheres for Oxidative Esterification of Biomass-Derived 5-Hydroxymethylfurfural
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One-pot synthesis of furan-2,5-dimethylcarboxylate (FDMC) from 5-hydroxymethylfurfural (HMF) is highly demanding for the commercial production of polyethylene furanoate (PEF). Herein, a direct synthesis of FDMC is reported from oxidative esterification of HMF using ultrafine CuO particles dispersed on nitrogen-doped hollow carbon nanospheres (CuO/N?C?HNSs) as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidizing and methylating reagent. The CuO/N?C?HNSs was prepared through a template protection-sacrifice strategy using SiO2 as a sacrificial template and histidine as the precursor for N and C. N-doping facilitated a strong interaction between the support and copper species, affording formation of CuO nanoparticles of less than 10 nm in size. By virtue of the highly dispersed CuO nanoparticles and a high BET surface area 373 m2/g, the CuO/N?C?HNSsshows excellent catalytic performance in the selective conversion of HMF into FDMC affording 93 % yield of the desired product with a TON value of 49. Furthermore, the oxidative esterification involving SP3C?H bond functionalization is also demonstrated using the same catalyst.
- Gupta, Shyam Sunder R.,Vinu, Ajayan,Kantam, Mannepalli Lakshmi
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p. 259 - 269
(2021/03/01)
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- Development of phenyltriazole thiol-based derivatives as highly potent inhibitors of DCN1-UBC12 interaction
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Defective in cullin neddylation 1(DCN1) is a co-E3 ligase that is important for cullin neddylation. Dysregulation of DCN1 highly correlates with the development of various cancers. Herein, from the initial high-throughput screening, a novel hit compound 5a containing a phenyltriazole thiol core (IC50 value of 0.95 μM for DCN1-UBC12 interaction) was discovered. Further structure-based optimization leads to the development of SK-464 (IC50 value of 26 nM). We found that SK-464 not only directly bound to DCN1 in vitro, but also engaged cellular DCN1, suppressed the neddylation of cullin3, and hindered the migration and invasion of two DCN1-overexpressed squamous carcinoma cell lines (KYSE70 and H2170). These findings indicate that SK-464 may be a novel lead compound targeting DCN1-UBC12 interaction.
- Zhou, Wenjuan,Xu, Chenhao,Dong, Guanjun,Qiao, Hui,Yang, Jing,Liu, Hongmin,Ding, Lina,Sun, Kai,Zhao, Wen
-
-
- Cobalt Nanoparticles-Catalyzed Widely Applicable Successive C?C Bond Cleavage in Alcohols to Access Esters
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Selective cleavage and functionalization of C?C bonds have important applications in organic synthesis and biomass utilization. However, functionalization of C?C bonds by controlled cleavage remains difficult and challenging because they are inert. Herein, we describe an unprecedented efficient protocol for the breaking of successive C?C bonds in alcohols to form esters with one or multiple carbon atoms less using heterogeneous cobalt nanoparticles as catalyst with dioxygen as the oxidant. A wide range of alcohols including inactive long-chain alkyl aryl alcohols undergo smoothly successive cleavage of adjacent ?(C?C)n? bonds to afford the corresponding esters. The catalyst was used for seven times without any decrease in activity. Characterization and control experiments disclose that cobalt nanoparticles are responsible for the successive cleavage of C?C bonds to achieve excellent catalytic activity, while the presence of Co-Nx has just the opposite effect. Preliminary mechanistic studies reveal that a tandem sequence reaction is involved in this process.
- Dai, Wen,Gao, Shuang,Li, Guosong,Luo, Huihui,Lv, Ying,Shang, Sensen,Wang, Lianyue
-
supporting information
p. 19268 - 19274
(2020/08/26)
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- Nickel salt of phosphomolybdic acid as a bi-functional homogeneous recyclable catalyst for base free transformation of aldehyde into ester
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A Ni salt of phosphomolybdic acid (NiHPMA) was synthesized and characterized by various physico-chemical techniques such as EDX, UV-Visible spectroscopy, FT-IR, Raman spectroscopy and XPS. FT-IR and Raman spectroscopy confirm the presence of Ni as a counter cation while UV-Visible and XPS studies to confirm the presence of Ni(ii) in the catalyst. The catalyst was evaluated for its bi-functional activity towards the tandem conversion of benzaldehyde to ethyl benzoate and it was found that very small amounts of Ni (2.64 × 10?3mmol) enhance the selectivity towards benzoate. A detailed mechanistic study was carried out by UV-Visible and Raman spectroscopy to confirm that both intermediate species, Mo-peroxo and Ni-oxo, are responsible for higher selectivity towards esters. Further, a study to determine the effect of addenda atoms (heteropoly acid) was also carried out. The catalyst was also found to be viable for a number of aldehydes under optimized conditions.
- Patel, Anjali,Patel, Jay
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p. 22146 - 22155
(2020/07/03)
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- Copper-catalyzed oxidative methyl-esterification of 5-hydroxymethylfurfural using TBHP as an oxidizing and methylating reagent: A new approach for the synthesis of furan-2,5-dimethylcarboxylate
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Catalytic conversion of 5-hydroxymethylfurfural (HMF) into furan-2,5-dimethylcarboxylate (FDMC) is of great significance in the production of polyethylene furanoate (PEF), a renewable biomass-derived polymer that can replace the fossil dependent polyethylene terephthalate (PET). Herein, for the first time, we report the synthesis of FDMC from oxidative methyl-esterification of HMF using tert-butyl hydroperoxide (TBHP) as an oxidizing and methylating reagent catalyzed by mesoporous alumina nanospheres-embedded with CuO nanoparticles (CuO/m-Al2O3). The CuO/m-Al2O3 catalysts with different copper contents were prepared by evaporation-induced self-assembly of a structure-directing agent (Pluronic P-123). The decomposition of P-123 during calcination in air results into the formation of a mesoporous structure with highly dispersed CuO nanoparticles. The as-prepared 6-CuO/m-Al2O3 exhibits excellent catalytic activity towards oxidative methyl-esterification of HMF into FDMC with 92% yield and turnover frequency (TOF) of 0.56 h?1. Furthermore, oxidative methyl-esterification of a range of substrates through SP3 C[sbnd]H bond functionalization has also been demonstrated using the same catalyst.
- Gupta, Shyam Sunder R.,Kantam, Mannepalli Lakshmi,Vinu, Ajayan
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p. 259 - 269
(2020/06/27)
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- Palladium-Catalyzed, Copper(I)-Promoted Methoxycarbonylation of Arylboronic Acids with O-Methyl S-Aryl Thiocarbonates
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Here, we report O-methyl S-aryl thiocarbonates as a versatile esterification reagent for palladium-catalyzed methoxycarbonylation of arylboronic acid in the presence of copper(I) thiophene-2-carboxylate (CuTC). The reaction condition is mild, and a variety of substituents including sensitive-Cl,-Br, and free-NH2 could be tolerated. Further applications in the late-stage esterification of some pharmaceutical drugs demonstrate the broad utility of this method.
- Cao, Ya-Fang,Li, Ling-Jun,Liu, Min,Xu, Hui,Dai, Hui-Xiong
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p. 4475 - 4481
(2020/04/10)
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- CHROMEN-4-ONE DERIVATIVES FOR THE TREATMENT AND PROPHYLAXIS OF HEPATITIS B VIRUS DISEASE
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The present invention provides novel compounds having the general formula (I) wherein R1 to R6, and m are as described herein, compositions including the compounds and methods of using the compounds.
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Page/Page column 97
(2020/05/21)
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- Synthesis, biological evaluation of benzothiazole derivatives bearing a 1,3,4-oxadiazole moiety as potential anti-oxidant and anti-inflammatory agents
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Twenty benzothiazole derivatives bearing a 1,3,4-oxadiazole moiety were synthesized and evaluated for their anti-oxidant and anti-inflammatory activities. Among these compounds, 8h and 8l were appeared to have high radical scavenging efficacies as 0.05 ± 0.02 and 0.07 ± 0.03 mmol/L of IC50 values in ABTS+[rad] bioassay, respectively. In anti-inflammatory tests, compound 8h displayed good activity with 57.35% inhibition after intraperitoneal administration, which was more potent than the reference drug (indomethacin). Molecular modeling studies were performed to investigate the binding mode of the representative compound 8h into COX-2 enzyme. In vitro enzyme study implied that compound 8h exerted its anti-inflammatory activity through COX-2 inhibition.
- Bai, Xue-Qian,Cui, Ming-Yue,Li, Chun-Shi,Liang, Cheng-Wu,Song, Ze-Wen,Wang, Hui-Yan,Zhang, Tian-Yi,Zheng, Xian-Jing
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- Discovery of [1,2,4]triazole derivatives as new metallo-β-lactamase inhibitors
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The emergence and spread of metallo-β-lactamase (MBL)-mediated resistance to β-lactam antibacterials has already threatened the global public health. A clinically useful MBL inhibitor that can reverse β-lactam resistance has not been established yet. We here report a series of [1,2,4]triazole derivatives and analogs, which displayed inhibition to the clinically relevant subclass B1 (Verona integron-encoded MBL-2) VIM-2. 3-(4-Bromophenyl)-6,7-dihydro-5H-[1,2,4]triazolo [3,4-b][1,3]thiazine (5l) manifested the most potent inhibition with an IC50 (half-maximal inhibitory concentration) value of 38.36 μM. Investigations of 5l against other B1 MBLs and the serine β-lactamases (SBLs) revealed the selectivity to VIM-2. Molecular docking analyses suggested that 5l bound to the VIM-2 active site via the triazole involving zinc coordination and made hydrophobic interactions with the residues Phe61 and Tyr67 on the flexible L1 loop. This work provided new triazole-based MBL inhibitors and may aid efforts to develop new types of inhibitors combating MBL-mediated resistance.
- Yuan, Chen,Yan, Jie,Song, Chen,Yang, Fan,Li, Chao,Wang, Cheng,Su, Huiling,Chen, Wei,Wang, Lijiao,Wang, Zhouyu,Qian, Shan,Yang, Lingling
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- Woody species: A new bio-based material for dual Ca/Mg catalysis with remarkable Lewis acidity properties
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Advances in green catalysis have promoted the development of ecocatalysis encountered in most of the main transformations of organic chemistry. Taking advantage of the remarkable capacity of certain plants to hyperaccumulate transition metals into shoots or roots, we have addressed the direct use of metals derived from contaminated plant wastes as supported Lewis acid catalysts, coupling agents, oxidative and reducing catalysts in green chemistry. This approach constituted the first example of chemical catalyst based on phytotechnologies. Herein, we show that the concept can be extended to common and abundant plant species that are surprisingly appropriated for chemical catalysis. We present that willow, birch, plane and linden trees can be used to produce bio-based and original Lewis acid catalysts. The catalytic potential of these species will be illustrated through two representative transformations, acetalisation and oxidative esterification. Thanks to their original polymetallic composition, ecocatalysts provided better results compared to classical metal chlorides such as MgCl2, CaCl2 or ZnCl2. This illustrates the interest of the ecocatalysis and is incorporated within the green and sustainable chemistry concept.
- Deyris, Pierre-Alexandre,Adler, Pauline,Petit, Eddy,Legrand, Yves-Marie,Grison, Claude
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p. 3133 - 3142
(2019/06/18)
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- SAR Studies on Aromatic Acylhydrazone-Based Inhibitors of Fungal Sphingolipid Synthesis as Next-Generation Antifungal Agents
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Recently, the fungal sphingolipid glucosylceramide (GlcCer) synthesis has emerged as a highly promising new target for drug discovery of next-generation antifungal agents, and we found two aromatic acylhydrazones as effective inhibitors of GlcCer synthesis based on HTP screening. In the present work, we have designed libraries of new aromatic acylhydrazones, evaluated their antifungal activities (MIC80 and time-kill profile) against C. neoformans, and performed an extensive SAR study, which led to the identification of five promising lead compounds, exhibiting excellent fungicidal activities with very large selectivity index. Moreover, two compounds demonstrated broad spectrum antifungal activity against six other clinically relevant fungal strains. These five lead compounds were examined for their synergism/cooperativity with five clinical drugs against seven fungal strains, and very encouraging results were obtained; e.g., the combination of all five lead compounds with voriconazole exhibited either synergistic or additive effect to all seven fungal strains.
- Del Poeta, Maurizio,Haranahalli, Krupanandan,Lazzarini, Cristina,Mallamo, John,McCarthy, J. Brian,Ojima, Iwao,Pathiranage, Senuri,Sun, Yi,Zambito, Julia
-
-
- METHOD FOR THE SYNTHESIS AND PURIFICATION OF ARYL ACID ESTERS
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The general inventive concepts are directed to the discovery that certain aryl acids can be esterified under particular conditions to provide the resulting ester as a solid that precipitates in good yield from the reaction mixture. The esters may then be isolated and purified with relative ease. Accordingly, a method for the esterification, isolation, and purification of aryl acids is provided.
- -
-
Paragraph 0029-0030
(2019/10/17)
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- A biocatalytic method for the chemoselective aerobic oxidation of aldehydes to carboxylic acids
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Herein, we present a study on the oxidation of aldehydes to carboxylic acids using three recombinant aldehyde dehydrogenases (ALDHs). The ALDHs were used in purified form with a nicotinamide oxidase (NOx), which recycles the catalytic NAD+ at the expense of dioxygen (air at atmospheric pressure). The reaction was studied also with lyophilised whole cell as well as resting cell biocatalysts for more convenient practical application. The optimised biocatalytic oxidation runs in phosphate buffer at pH 8.5 and at 40 °C. From a set of sixty-one aliphatic, aryl-Aliphatic, benzylic, hetero-Aromatic and bicyclic aldehydes, fifty were converted with elevated yield (up to >99%). The exceptions were a few ortho-substituted benzaldehydes, bicyclic heteroaromatic aldehydes and 2-phenylpropanal. In all cases, the expected carboxylic acid was shown to be the only product (>99% chemoselectivity). Other oxidisable functionalities within the same molecule (e.g. hydroxyl, alkene, and heteroaromatic nitrogen or sulphur atoms) remained untouched. The reaction was scaled for the oxidation of 5-(hydroxymethyl)furfural (2 g), a bio-based starting material, to afford 5-(hydroxymethyl)furoic acid in 61% isolated yield. The new biocatalytic method avoids the use of toxic or unsafe oxidants, strong acids or bases, or undesired solvents. It shows applicability across a wide range of substrates, and retains perfect chemoselectivity. Alternative oxidisable groups were not converted, and other classical side-reactions (e.g. halogenation of unsaturated functionalities, Dakin-Type oxidation) did not occur. In comparison to other established enzymatic methods such as the use of oxidases (where the concomitant oxidation of alcohols and aldehydes is common), ALDHs offer greatly improved selectivity.
- Knaus, Tanja,Tseliou, Vasilis,Humphreys, Luke D.,Scrutton, Nigel S.,Mutti, Francesco G.
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supporting information
p. 3931 - 3943
(2018/09/11)
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- Formation of esters and amides via metal-free Csp2-Csp3 bond cleavage of α-nitro ketone: Mechanistic insight to the reaction pathway
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A catalyst free protocol for hucleophilic Csp2-Csp3 bond cleavage of a-nitroketone has been achieved for the formation of C-O and C-N bond. A series of differently substituted a-nitroketones could be selectively cleaved and converted into corresponding esters and tosylamides in presence of alcohols and bromamine-T respectively. Mechanism of the C-C bond cleavage has been proposed by identifying different reaction intermediates using IR and NMR spectroscopic methods.
- Sarma, Manas Jyoti,Phukan, Prodeep
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p. 523 - 533
(2019/05/21)
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- Reevaluating the Substrate Specificity of the L-Type Amino Acid Transporter (LAT1)
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The L-type amino acid transporter 1 (LAT1, SLC7A5) transports essential amino acids across the blood-brain barrier (BBB) and into cancer cells. To utilize LAT1 for drug delivery, potent amino acid promoieties are desired, as prodrugs must compete with millimolar concentrations of endogenous amino acids. To better understand ligand-transporter interactions that could improve potency, we developed structural LAT1 models to guide the design of substituted analogues of phenylalanine and histidine. Furthermore, we evaluated the structure-activity relationship (SAR) for both enantiomers of naturally occurring LAT1 substrates. Analogues were tested in cis-inhibition and trans-stimulation cell assays to determine potency and uptake rate. Surprisingly, LAT1 can transport amino acid-like substrates with wide-ranging polarities including those containing ionizable substituents. Additionally, the rate of LAT1 transport was generally nonstereoselective even though enantiomers likely exhibit different binding modes. Our findings have broad implications to the development of new treatments for brain disorders and cancer.
- Chien, Huan-Chieh,Colas, Claire,Finke, Karissa,Springer, Seth,Stoner, Laura,Zur, Arik A.,Venteicher, Brooklynn,Campbell, Jerome,Hall, Colton,Flint, Andrew,Augustyn, Evan,Hernandez, Christopher,Heeren, Nathan,Hansen, Logan,Anthony, Abby,Bauer, Justine,Fotiadis, Dimitrios,Schlessinger, Avner,Giacomini, Kathleen M.,Thomas, Allen A.
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supporting information
p. 7358 - 7373
(2018/08/06)
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- PROCESS FOR THE PREPARATION OF ORGANIC BROMIDES
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The present invention provides a process for the preparation of organic bromides, by a radical bromodecarboxylation of carboxylic acids with a bromoisocyanurate.
- -
-
Paragraph 00139; 00141; 00158
(2017/07/28)
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- Oxalic acid as the: In situ carbon monoxide generator in palladium-catalyzed hydroxycarbonylation of arylhalides
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An efficient palladium-catalyzed hydroxycarbonylation reaction of arylhalides using oxalic acid as a CO source has been developed. The reaction features high safety, low catalyst loading, and a broad substrate scope, and provides a safe and tractable approach to access a variety of aromatic carboxylic acid compounds. Mechanistic studies revealed the decomposition pattern of oxalic acid.
- Shao, Changdong,Lu, Ailan,Wang, Xiaoling,Zhou, Bo,Guan, Xiaohong,Zhang, Yanghui
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p. 5033 - 5040
(2017/07/10)
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- Preparation method of m-cyanomethyl methyl benzoate
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The invention discloses a preparation method of m-cyanomethyl methyl benzoate. According to the method, m-bromobenzoic acid is used as a starting raw material; the m-bromine methyl methyl benzoate is prepared through esterification; m-methoxy formyl phenethyl alcohol is obtained and prepared through Grignard reaction; through oxidization, the m-methoxy formyl phenylacetic acid is prepared; through amidation and dewatering, the m-cyanomethyl methyl benzoate is finally prepared. The preparation method provided by the invention has the advantages that the design is ingenious; the route is novel; the raw materials have low price and can be easily obtained; the process is simple; the implementation is easy; the yield is high; the purity of the obtained final product is high; the quality is high; no dangerous process exists; the extremely toxic substances of cyanides and expensive cyaniding reagents used in the conventional synthesis are avoided; the requirements on the equipment are simple; the production difficulty and the production cost investment are reduced; the industrial production can be favorably realized; the economic benefits are good.
- -
-
Paragraph 0005; 0012
(2017/08/30)
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- Design, synthesis, and negative inotropic evaluation of 4-phenyl-1H-1,2,4-triazol-5(4H)-one derivatives containing triazole or piperazine moieties
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In this study, four novel series of 4-phenyl-1H-1,2,4-triazol-5(4H)-one derivatives containing triazole or piperazine moieties were designed, synthesized, and evaluated for negative inotropic activity by measuring the left atrium stroke volume in isolated rabbit heart preparations. Almost all of the compounds showed an ability to moderate the cardiac workload by decreasing the heart rate and contractility. Among them, 7h was found to be the most potent with a change in stroke volume of ?48.22?±?0.36% at a concentration of 3?×?10?5?mol/L (metoprolol: ?9.74?±?0.14%). The cytotoxicity of these compounds was evaluated using the human cervical cancer cell line HeLa, the liver cancer cell line Hep3B, and the human normal hepatic cell line LO2. A preliminary study of the mechanism of action for the compound 7h on the regulation of atrial dynamics with ATP-sensitive K+ channel and L-type Ca2+ channel blockers glibenclamide and nifedipine was performed in the isolated perfused beating rabbit atria.
- Wei, Zhi-Yu,Cui, Bai-Ri,Cui, Xun,Wu, Yan-Ling,Fu, Yang,Liu, Li-Ping,Piao, Hu-Ri
-
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- 3-PHOSPHOGLYCERATE DEHYDROGENASE INHIBITORS AND USES THEREOF
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The present invention provides compounds, compositions thereof, and methods of using the same.
- -
-
Paragraph 00323; 00324; 00325
(2017/09/27)
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- Chemoselective dehydrogenative esterification of aldehydes and alcohols with a dimeric rhodium(II) catalyst
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Dehydrogenative cross-coupling of aldehydes with alcohols as well as dehydrogentive cross-coupling of primary alcohols to produce esters have been developed using a Rh-terpyridine catalyst. The catalyst demonstrates broad substrate scope and good functional group tolerance, affording esters highly selectively. The high chemoselectivity of the catalyst stems from its preference for dehydrogenation of benzylic alcohols over aliphatic ones. Preliminary mechanistic studies suggest that the active catalyst is a dimeric Rh(ii) species, operating via a mechanism involving metal-base-metal cooperativity.
- Cheng, Junjie,Zhu, Meijuan,Wang, Chao,Li, Junjun,Jiang, Xue,Wei, Yawen,Tang, Weijun,Xue, Dong,Xiao, Jianliang
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p. 4428 - 4434
(2016/07/07)
-
- Gold nanoparticle-decorated graphene oxide: Synthesis and application in oxidation reactions under benign conditions
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Gold nanoparticles (~13?nm, 4?wt% Au) dispersed on reduced graphene oxide (Au/rGO) surface were prepared via the reduction of gold (III) chloride using sodium citrate on reduced graphene oxide support. The chemical, morphological, and size analyses of Au/rGO by XRD, XPS, TEM, HR-TEM/EDS, AAS, and Raman spectroscopy revealed that the hybrid material comprised of a well-defined rGO support decorated with gold nanoparticles. The ensuing catalyst was evaluated for the oxidation of ethyl benzenes (yields up to 95%) and oxidative esterification of aldehydes (73–97%) using oxygen as an environmentally friendly oxidant in good to excellent yields; reusable and recyclable catalyst displayed high activity without the use of toxic organic solvents.
- Pocklanova, Radka,Gawande, Manoj B.,Rathi, Anuj K.,Gawande, Manoj B.,Datta, Kasibhatta Kumara Ramanatha,Ranc, Vaclav,Cepe, Klara,Petr, Martin,Varma, Rajender S.,Kvitek, Libor,Zboril, Radek
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p. 121 - 127
(2016/09/07)
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- NOVEL SINGLE STEP ESTERIFICATION PROCESS OF ALDEHYDES USING A HETEROGENEOUS CATALYST
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The present invention relates to a novel simple, efficient and single-step process for esterification of aldehydes using a heterogeneous catalyst with high yields. More particularly, the present invention relates to a novel simple, efficient and single-step process for esterification of aldehydes using Titanium superoxide with greater than 80% yields.
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Page/Page column 7; 16; 17
(2016/06/20)
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- Synthesis method for methyl-3'-bromine-[1,1'-biphenyl]-3-carboxylic acid formic acid
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The invention discloses a synthesis method for methyl-3'-bromine-[1,1'-biphenyl]-3-carboxylic acid formic acid, and belongs to the technical field of organic chemistry.The method comprises the steps that benzene is used as a raw material and mixed with acetic anhydride and aluminum chloride for a reaction, then, concentrated nitric acid and concentrated sulfuric acid are added for a nitration reaction, the reaction product is sufficiently mixed with liquid bromine under the effect of iron powder, the mixture is placed in a reaction kettle, dimethyl carbonate and zirconium dioxide powder are added, boron trifluoride is introduced for a reaction, heating distillation is carried out under the oxidation of potassium permanganate and glacial acetic acid, ice water and zinc powder are added and mixed, standing decompression and suction filtration are performed, and the product is obtained.The synthesis method has the advantages that synthetic conditions are simple, few by-products are produced in the synthetic process, the cost is 5% or more lower than the cost of other methods, the obtained product is high in purity, and the yield is 15.5% or more higher than that of the other methods.
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-
- Pd-Supported on N-doped carbon: Improved heterogeneous catalyst for base-free alkoxycarbonylation of aryl iodides
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Novel Pd-based heterogeneous catalysts were prepared through immobilization of Pd(OAc)2/phenanthroline on carbon and subsequent pyrolysis. The most active catalyst was characterized by TEM, XPS and XRD techniques and was successfully used for the base-free methoxycarbonylation of aryl iodides. Notably, no metal contamination (detection limit 0.5 ppm) in the final products was observed.
- Ziccarelli, Ida,Neumann, Helfried,Kreyenschulte, Carsten,Gabriele, Bartolo,Beller, Matthias
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supporting information
p. 12729 - 12732
(2016/11/02)
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- Design, synthesis and antibacterial activity of isatin derivatives as FtsZ inhibitors
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Seven isatin derivatives have been designed, and their chemical structures were characterized by single crystal X-ray diffraction studies, 1H NMR, MS, and elemental analysis. Structural stabilization followed by intramolecular as well as intermolecular H-bonds makes these molecules as perfect examples in molecular recognition with self-complementary donor and acceptor units within a single molecule. These compounds were evaluated for antimicrobial activities. Docking simulations have been performed to position compounds into the FtsZ active site to determine their probable binding models. All of the compounds exhibited better antibacterial activities. Interestingly, compound 5c and 5d exhibited better antibacterial activities with IC50 values of 0.03 and 0.05 μmol/mL against Staphylococcus aureus, respectively. Compound 5g displays antibacterial activity with IC50 values of 0.672 and 0.830 μmol/mL against Escherichia coli and Pseudomonas aeruginosa, respectively.
- Lian, Zhi-Min,Sun, Juan,Zhu, Hai-Liang
-
-
- An efficient nonconventional glycerol-based solid acid catalyzed synthesis and biological evaluation of phosphonate conjugates of 1,2,4-triazole thiones
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A series of diethyl (3-((5-aryl-1H-1,2,4-triazol-3-yl)thio)propyl)phos-phonates (7a-t) has been synthesized in excellent yields by coupling diethyl (3-bromopropyl)phosphonate and 5-aryl-1H- 1,2,4-triazol-3-thiones employing an efficient, green and nonconventional heterogeneous SO3Hcarbon catalyst derived from glycerol. In addition, a facile and green approach for the esterification of carboxylic acids by utilizing glycerol-based solid acid catalyst has been reported. Structures of the synthesized compounds were characterized by IR, NMR and HRMS studies. These triazole derivatives were screened for their in vitro cytotoxicity using the standard MTT (3-(4,5-dimethylthiazol-2- yl)-2,5-diphenyltetra-zolium bromide) assay against a panel of five different human cancer cell lines (HeLa: Cervix, A549: Lung, A375: Skin, MDA-MB-231: Breast and T98G: Brain). The antimicrobial activities of the synthesized compounds were investigated against four bacterial strains: Bacillus subtilis, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and three fungal strains: Aspergillus Niger, Aspergillus terreus, Aspergillus fumigatus. Preliminary results indicate that the compound 7f displayed maximum anticancer activity and the compounds 7d, 7e, 7f, 7m and 7q exhibited moderate antibacterial activity. The compounds 7g, 7h, 7o and 7p showed good antifungal activity with high inhibition zone diameter compared to the standard drug.
- Murty, Madugula S.R.,Katiki, Mohana R.,Rao, Busam R.,Narayanan, Sai S.,Anto, Ruby J.,Buddana, Sudhreer K.,Prakasham, Reddy S.,Devi, Bethala L.A.P.,Prasad, Rachapudi B.N.
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p. 968 - 981
(2016/10/31)
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- Titanium superoxide-a stable recyclable heterogeneous catalyst for oxidative esterification of aldehydes with alkylarenes or alcohols using TBHP as an oxidant
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Titanium superoxide efficiently catalysed the oxidative esterification of aldehydes with alkylarenes or alcohols, under truly heterogeneous conditions, to afford the corresponding benzyl and alkyl esters in excellent yields. Mechanistic studies have established that this "one pot" direct oxidative esterification process proceeds through a radical pathway, proven by a FTIR spectral study of a titanium superoxide-aldehyde complex as well as spin trapping experiments with TEMPO. The intramolecular version of this protocol has been successfully demonstrated in the concise synthesis of 3-butylphthalide, an anti-convulsant drug.
- Dey, Soumen,Gadakh, Sunita K.,Sudalai
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p. 10631 - 10640
(2015/11/17)
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- Magnetic Co3O4/reduced graphene oxide nanocomposite as a superior heterogeneous catalyst for one-pot oxidative esterification of aldehydes to methyl esters
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A magnetically separable hybrid material consisting of Co3O4 nanoparticles supported on reduced graphene oxide (Co3O4/rGO) was synthesized through a simple co-reduction process of graphene oxide (GO) and cobalt chloride (CoCl2) using sodium borohydride (NaBH4). The Co3O4/rGO heterogeneous catalyst exhibited a high-performance for the oxidative esterification of aldehydes to the corresponding methyl esters using tert-butyl hydroperoxide (TBHP) as an oxidant. Owing to the synergistic effect of rGO support, the hybrid catalyst exhibited superior catalytic activity to the corresponding cobalt oxide catalyst. Importantly, the synthesized hybrid possesses good magnetic properties, which enable facile recovery of the catalyst by using an external magnet.
- Panwar, Vineeta,Al-Nafiey, Amer,Addad, Ahmed,Sieber, Brigitte,Roussel, Pascal,Boukherroub, Rabah,Jain, Suman L.
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p. 88567 - 88573
(2015/11/09)
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- NOVEL BIPHENYL DERIVATIVE OR PHARMACEUTICALLY ACCEPTABLE SALT THEREOF, AND PHARMACEUTICAL COMPOSITION FOR PREVENTING OR TREATING INFLAMMATORY DISEASES OR AUTOIMMUNE DISEASES COMPRISING THE SAME AS ACTIVE INGREDIENT
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The present invention relates to a novel biphenyl derivative or a pharmaceutically acceptable salt thereof, a pharmaceutical composition for preventing or treating inflammatory diseases or autoimmune diseases comprising the same as an active ingredient, and methods for treating inflammatory disease or autoimmune diseases with the pharmaceutical composition. Novel biphenyl derivatives according to the present invention promote the phagocytosis of macrophages and inhibit the chemotaxis to exhibit excellent inflammation terminating and anti-inflammatory effects and thus can be effectively used as therapeutic agents for inflammatory diseases or autoimmune diseases.
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Paragraph 66; 67
(2015/11/18)
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- Formation of new C-O and C-N bonds via base promoted Csp2-Csp3 bond cleavage of α-nitro ketone
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A catalyst free protocol has been developed for nucleophilic Csp2-Csp3 bond cleavage of α-nitroketone in the presence of potassium carbonate to create new C-O and C-N bonds. A series of different substituted α-nitroketones could be selectively cleaved and converted into corresponding esters and tosylamides in the presence of alcohols and bromamine-T, respectively.
- Sarma, Manas Jyoti,Borah, Arun Jyoti,Rajbongshi, Kamal Krishna,Phukan, Prodeep
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supporting information
p. 7008 - 7011
(2015/11/27)
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- Efficient synthesis of amides and esters from alcohols under aerobic ambient conditions catalyzed by a Au/mesoporous Al2O3 nanocatalyst
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An efficient heterogeneous Au/mesoporous alumina nanocatalyst has been successfully developed for the synthesis of amides and esters from simple building blocks of readily available alcohols and amines. The processes were simple and were performed at room temperature and atmospheric pressure of O2 to form the desired products with up to 97% isolated yield. The ability of Au/mesoporous alumina to catalyze these reactions under ambient conditions further enhances the sustainability of these chemical processes. Furthermore, the nanocatalyst was stable to air and water and could be recovered and reused easily. The enhanced catalytic activity of Au/mesoporous alumina might be attributed to the presence of negatively charged Au nanoparticles that could promote oxidation processes as well as the stability of the mesoporous alumina support calcined at a high temperature of 800°C. Gold for green: Gold nanoparticles supported on mesoporous alumina catalyze the efficient synthesis of amides and esters from simple building blocks of readily available alcohols and amines under ambient aerobic reaction conditions (R1=aryl, alkyl, and R2=H, alkyl).
- Chng, Leng Leng,Yang, Jinhua,Ying, Jackie Y.
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p. 1916 - 1925
(2015/06/16)
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- Rhodium-catalyzed C-H activation of hydrazines leads to isoquinolones with tunable aggregation-induced emission properties
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Using an internally oxidizing directing group (DG) strategy, we report a RhIII-catalyzed synthesis of isoquinolones via C-H activation/annulation of benzoylhydrazines and alkynes. Tunable double cascade cyclization of benzoylhydrazines with two equivalents of alkynes led to tetracyclic amides. These N-heterocycles demonstrated adjustable AIE properties.
- Yu, Bole,Chen, Ying,Hong, Mei,Duan, Pingping,Gan, Shifeng,Chao, Hui,Zhao, Zujin,Zhao, Jing
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supporting information
p. 14365 - 14368
(2015/09/21)
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- Synthesis, anti-HIV activity and Molecular modeling study of 3-aryl-6-adamantylmethyl-[1,2,4] triazolo[3,4-b][1,3,4]thiadiazole derivatives
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A series of novel 3-aryl-6-adamantylmethyl-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazoles 6a-l were synthesized by a simple method with the aim of developing novel HIV non-nucleoside reverse transcriptase inhibitors. All the synthesized compounds were structurally confirmed by spectral analyses. The structure of 6a was unambiguously verified by X-ray structure determination. The synthesized compounds were evaluated for their anti-HIV activity and four analogs displayed moderate inhibitory activity with EC50 values ranging from 10.10 to 12.40 μg mL-1. Molecular docking of 6g with HIV-1 reverse transcriptase was studied to rationalize some structureactivity relationships (SARs).
- Khan, Mahmood-Ul-Hassan,Hameed, Shahid,Farman, Muhammad,Al-Masoudia, Najim A.,Stoeckli-Evans, Helen
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p. 609 - 616
(2016/02/18)
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- A catalyst-free protocol for direct oxidative esterification of alcohols and aldehydes
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A fast, simple, and efficient protocol for the direct conversion of alcohols and aldehydes to methyl ester has been developed using TsNBr2without any catalyst. The one pot reaction proceeds in the presence of a base at room temperature in methanol, to produce the corresponding methyl ester in high yield within a short time.
- Rajbongshi, Kamal Krishna,Sarma, Manas Jyoti,Phukan, Prodeep
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p. 5358 - 5360
(2015/01/08)
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- Heterogeneous Light-Mediated Reductive Dehalogenations and Cyclizations Utilizing Platinum Nanoparticles on Titania (PtNP@TiO2)
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The utility of platinum nanoparticles on titania (PtNP@TiO2) as a heterogeneous photoredox catalyst is evaluated using a series of reductive transformations. In comparison to TiO2 alone, TiO2 decorated with 0.2% PtNP shows enhanced efficiency, attributed to the NPs ability to both enhance light absorption and inhibit electron-hole pair recombination. Herein, we demonstrate that under an inert atmosphere and UVA/visible light irradiation a system consisting of our PtNP@TiO2 catalyst in conjunction with a sacrificial electron donor [diisopropylethylamine, (i-Pr)2NEt] can promote a variety of different reductive dehalogenations and cyclizations in moderate to excellent yields. In addition, the catalytic system is tolerant of many different functionalities and, due to its heterogeneous nature, holds the advantage of easy catalyst removal.
- McTiernan, Christopher D.,Pitre, Spencer P.,Ismaili, Hossein,Scaiano, Juan C.
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supporting information
p. 2819 - 2824
(2016/02/19)
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- Transition metal-free oxidative esterification of benzylic alcohols in aqueous medium
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Oxidative esterification of benzylic alcohols with a catalytic amount of HBr-H2O2 in aqueous medium under mild conditions is reported with a wide range of substrate scope for both benzylic and aliphatic alcohols. The conditions are also suitable for selective mono-esterification of ethylene glycol and glycerol. With catalytic amounts of HBr (20 mol%) and H2O2, the generation of reactive intermediate species BrOH has been ascertained by UV-visible spectra.
- Samanta, Supravat,Pappula, Venkatanarayana,Dinda, Milan,Adimurthy, Subbarayappa
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supporting information
p. 9453 - 9456
(2014/12/11)
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- Magnetic gold nanocatalyst (nanocat-Fe-Au): Catalytic applications for the oxidative esterification and hydrogen transfer reactions
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An efficient and sustainable protocol is described for the oxidative esterification of aldehydes and the reduction of aromatic nitro compounds that uses a magnetically separable and reusable maghemite-supported gold nanocatalyst (nanocat-Fe-Au) under mild conditions. The complex chemical, morphological, structural and size analyses, including e.g. XPS, HRTEM, in-field Moessbauer spectroscopy and HRTEM, revealed that the hybrid material is composed of a well-defined stoichiometric maghemite support (20-30 nm) decorated with ultrasmall (5-6 nm) gold nanoparticles. The hybrid catalytic system containing 4 wt% of nanogold has been generated using simple impregnation methods in aqueous medium from readily available starting materials and was recycled five times without any significant loss in catalytic activity; high yields, 40-95% and 83-94% for oxidative esterification and reduction reactions, respectively, were obtained. the Partner Organisations 2014.
- Gawande, Manoj B.,Rathi, Anuj K.,Tucek, Jiri,Safarova, Klara,Bundaleski, Nenad,Teodoro, Orlando M.N.D.,Kvitek, Libor,Varma, Rajender S.,Zboril, Radek
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p. 4137 - 4143
(2014/11/08)
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- Copper-catalyzed decarboxylative methylation of aromatic carboxylic acids with PhI(OAc)2
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The copper-catalyzed decarboxylative methylation of aromatic carboxylic acids was developed by using PhI(OAc)2 to provide a new strategy for the methylation of aryl acids through the decarboxylation of alkyl acids. The mechanism and the roles of each reactant in the reaction were investigated extensively. Copyright
- Jiang, Yuyu,Pan, Shulei,Zhang, Yanghui,Yu, Jingxun,Liu, Hongqiang
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supporting information
p. 2027 - 2031
(2014/04/17)
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- An insight into the mechanism of the aerobic oxidation of aldehydes catalyzed by N-heterocyclic carbenes
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N-Heterocyclic carbene catalysis for the aerobic oxidation and esterification of aromatic aldehydes was monitored by ESI-MS (MS/MS) and the key intermediates were intercepted and characterized using the charge-tag strategy.
- Bortolini,Chiappe,Fogagnolo,Giovannini,Massi,Pomelli,Ragno
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supporting information
p. 2008 - 2011
(2014/03/21)
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- Synthesis and evaluation of novel azoles as potent antifungal agents
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Using a rational approach to the design of antifungal agents, a series of azole agents with 1,3,4-oxadiazole side chains were designed and synthesized. The results of preliminary in vitro antifungal tests with eight human pathogenic compounds showed that all of the title compounds exhibited excellent activities against all of the tested fungi except Aspergillus fumigatus. Compounds 11e and 11f were found to be the most effective, with a minimum inhibitory concentration of 0.0039 μg/mL, followed by voriconazole, which has a MIC of 0.0625 μg/mL. The 1,3,4-oxadiazole side chain is not the major contributor but plays a role in eliciting the observed antifungal activity.
- Li, Liangjing,Ding, Hao,Wang, Baogang,Yu, Shichong,Zou, Yan,Chai, Xiaoyun,Wu, Qiuye
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p. 192 - 194
(2014/01/17)
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- Mechanistic investigation of the oxidation of hydrazides: Implications for the activation of the TB drug isoniazid
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Aryl hydrazides are oxidised to acyl radicals through a mechanism involving diimide intermediates that are prone to nucleophilic acyl substitution. This oxidation occurs regardless of the oxidant involved, however there is no evidence that the acyl radical formed undergoes further oxidation to the corresponding acylium ion, even in the presence of strong oxidants. This study may provide insight into the mechanism of isoniazid resistance in Mycobacterium tuberculosis. The Royal Society of Chemistry.
- Amos, Ruth I. J.,Gourlay, Brendon S.,Yates, Brian F.,Schiesser, Carl H.,Lewis, Trevor W.,Smith, Jason A.
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p. 170 - 176
(2013/02/23)
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- Nickel(II) catalyzed oxidation of aldehyde derivatives to their carboxylic acid or ester analogs
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Diverse aromatic, aliphatic and conjugated aldehydes were converted to the corresponding carboxylic acid or methyl ester derivatives with 30 % H 2O2 as the oxidant in the presence of a catalytic amount of nickel(II) complex as precursor. Ni(II) complex was prepared from the reaction of methyl 2-{3-[(E)-4-oxopent-2-en-2-ylamino]propylamino}cyclopent-1- enecarbodithioate as a tetra-dentate ligand with Ni(II) acetate in 60 % yield and was tested for its catalytic activity in the oxidation reaction. The prepared complex was characterized on the basis of 1H NMR, FT-IR, MASS, and CHN analysis. Aldehydes were oxidized to their corresponding carboxylic acid in acetonitrile as solvent and were converted to methyl esters in methanol as solvent. For all substrates, a considerable rate enhancement was observed. The present methodology offers several advantages such as applicability to a wide range of aldehydes, convenient work-up, mild reaction conditions, and good yields and reasonable time of the reactions. Graphical Abstract: [Figure not available: see fulltext.]
- Esfandiari, Hadi,Jameh-Bozorghi, Saeed,Esmaielzadeh, Sheida,Shafiee, Mohammad Reza Mohammad,Ghashang, Majid
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p. 3319 - 3325
(2013/09/23)
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- N-Heterocyclic carbene catalyzed esterification of aromatic aldehydes with alcohols under aerobic conditions
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A simple, organocatalytic procedure for the direct oxidative esterification of a variety of aromatic aldehydes with alcohols has been described that affords the corresponding aromatic esters in high yields. The method employs N-heterocyclic carbenes as catalysts and molecular O2 as an oxidant under ambient conditions.
- Kiran, I. N. Chaithanya,Lalwani, Komal,Sudalai, Arumugam
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p. 1695 - 1698
(2013/03/13)
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- Synthesis, antibacterial activities, and 3d-qsar of sulfone derivatives containing 1, 3, 4-oxadiazole moiety
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A series of sulfone derivatives containing 1, 3, 4-oxadiazole moiety were prepared and evaluated for their antibacterial activities by the turbidimeter test. Most compounds inhibited growth of Ralstonia solanacearum (R. solanacearum) from tomato and tobacco bacterial wilt with high potency, among which compounds 5a and 5b exhibited the most potent inhibition against R. solanacearum from tomato and tobacco bacterial wilts with EC50 values of 19.77 and 8.29 μg/mL, respectively. Our results also demonstrated that 5a, 5b, and a number of other compounds were more potent than commercial bactericides Kocide 3000 and Thiodiazole Copper, which inhibited R. solanacearum from tomato bacterial wilt with EC50 values of 93.59 and 99.80 μg/mL and tobacco bacterial wilt with EC50 values of 45.91 and 216.70 μg/mL, respectively. The structure-activity relationship (SAR) of compounds was studied using three-dimensional quantitative structure-activity relationship (3D-QSAR) models created by comparative molecular field analysis (CoMFA) and comparative molecular similarity index analysis (CoMSIA) based on compound bioactivities against tomato and tobacco bacterial wilts. The 3D-QSAR models effectively predicted the correlation between inhibitory activity and steric-electrostatic properties of compounds.
- Li, Pei,Yin, Juan,Xu, Weiming,Wu, Jian,He, Ming,Hu, Deyu,Yang, Song,Song, Baoan
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p. 546 - 556
(2013/11/06)
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- A new recoverable Au(III) catalyst supported on magnetic polymer nanocomposite for aromatic bromination
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This Letter presents a facile alternative synthesis of a recoverable Au(III) catalyst supported on Fe3O4@SiO 2~MPS grafted by poly(N-vinyl-2-pyrrolidone) (PVP). The solid magnetic support was prepared by anchoring 3-methacryloxypropyltrimethoxysilane (MPS) onto the Fe3O4@SiO2 surfaces followed by free radical polymerization with N-vinyl-2-pyrrolidone. Au(III) was immobilized onto the magnetic support in aqueous media to afford Au(III)/Fe 3O4@SiO2~PVP (catalyst 1). Catalyst 1 was characterized by FT-IR, TEM, VSM, TGA, XRD, and ICP-AES. The amount of Au in catalyst 1 was measured to be 0.64 wt % by ICP-AES. This newly prepared catalyst can catalyze the aromatic bromination reaction with comparable activity as homogeneous AuCl3. Moreover, the supported catalyst is easy to recover and can be used in four cycles without apparent loss of activity.
- Li, Bai,Gao, Linfeng,Bian, Fengling,Yu, Wei
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supporting information
p. 1063 - 1066
(2013/04/10)
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- Tribromoisocyanuric acid in trifluoroacetic acid: An efficient system for smooth brominating of moderately deactivated arenes
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Moderately deactivated arenes are efficiently brominated by the reaction with tribromoisocyanuric acid (0.34 mol equiv) in trifluoroacetic acid at room temperature in 48-85% isolated yield. This medium avoids the polybromination of the substrate, observed in the same reaction performed in 98% H 2SO4. Georg Thieme Verlag Stuttgart · New York.
- De Almeida, Leonardo S.,De Mattos, Marcioc. S.,Esteves, Pierre M.
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p. 603 - 606
(2013/04/10)
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- Engaging unactivated alkyl, alkenyl and aryl iodides in visible-light-mediated free radical reactions
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Radical reactions are a powerful class of chemical transformations. However, the formation of radical species to initiate these reactions has often required the use of stoichiometric amounts of toxic reagents, such as tributyltin hydride. Recently, the use of visible-light-mediated photoredox catalysis to generate radical species has become popular, but the scope of these radical precursors has been limited. Here, we describe the identification of reaction conditions under which photocatalysts such as fac-Ir(ppy) 3 can be utilized to form radicals from unactivated alkyl, alkenyl and aryl iodides. The generated radicals undergo reduction via hydrogen atom abstraction or reductive cyclization. The reaction protocol utilizes only inexpensive reagents, occurs under mild reaction conditions, and shows exceptional functional group tolerance. Reaction efficiency is maintained upon scale-up and decreased catalyst loading, and the reaction time can be significantly shortened when the reaction is performed in a flow reactor.
- Nguyen, John D.,D'Amato, Erica M.,Narayanam, Jagan M. R.,Stephenson, Corey R. J.
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p. 854 - 859
(2012/11/07)
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