- Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst
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An original cooperative photoredox catalytic system, [RuII(trpy)(bpy)(H2O)][3,3′-Co(1,2-C2B9H11)2]2 (C4; trpy = terpyridine and bpy = bipyridine), has been synthesized. In this system, the photoredox metallacarborane catalyst [3,3′-Co(1,2-C2B9H11)2]- ([1]-) and the oxidation catalyst [RuII(trpy)(bpy)(H2O)]2+ (C2′) are linked by noncovalent interactions and not through covalent bonds. The noncovalent interactions to a large degree persist even after water dissolution. This represents a step ahead in cooperativity avoiding costly covalent bonding. Recrystallization of C4 in acetonitrile leads to the substitution of water by the acetonitrile ligand and the formation of complex [RuII(trpy)(bpy)(CH3CN)][3,3′-Co(1,2-C2B9H11)2]2 (C5), structurally characterized. A significant electronic coupling between C2′ and [1]- was first sensed in electrochemical studies in water. The CoIV/III redox couple in water differed by 170 mV when [1]- had Na+ as a cation versus when the ruthenium complex was the cation. This cooperative system leads to an efficient catalyst for the photooxidation of alcohols in water, through a proton-coupled electron-transfer process. We have highlighted the capacity of C4 to perform as an excellent cooperative photoredox catalyst in the photooxidation of alcohols in water at room temperature under UV irradiation, using 0.005 mol % catalyst. A high turnover number (TON = 20000) has been observed. The hybrid system C4 displays a better catalytic performance than the separated mixtures of C2′ and Na[1], with the same concentrations and ratios of Ru/Co, proving the history relevance of the photocatalyst. Cooperative systems with this type of interaction have not been described and represent a step forward in getting cooperativity avoiding costly covalent bonding. A possible mechanism has been proposed.
- Guerrero, Isabel,Vi?as, Clara,Fontrodona, Xavier,Romero, Isabel,Teixidor, Francesc
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p. 8898 - 8907
(2021/06/28)
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- Metallacarboranes as Photoredox Catalysts in Water
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Metallacarboranes with the shape of the Greek letter θ, such as [Co(C2B9H11)2]?, were tested, for the first time, as efficient photoredox catalysts in the oxidation of aromatic and aliphatic alcohols in water. Their efficiency is linked to their high solubility in water, their high oxidizing power (Co4+/3+), and their absence of fluorescence on excitation, among others. In most of the studied examples, using a catalyst load of 0.4 mol % gave high yields of 90–95 % with selectivity greater than 99 %. By reducing the catalyst load to 0.01 mol %, quantitative conversion of reactants to products was achieved, in some cases with greater than 99 % yield, high catalyst efficiency reaching a turnover number of 10 000, and a higher yield with a 45 times lower concentration of catalyst. The metallacarboranes can be recovered easily by precipitation on addition of [NMe4]Cl. A pathway for the photoredox-catalyzed oxidation of alcohols is proposed.
- Guerrero, Isabel,Kelemen, Zsolt,Romero, Isabel,Teixidor, Francesc,Vi?as, Clara
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p. 5027 - 5036
(2020/04/22)
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- N-(3-(2-(4-CHLOROPHENOXY)ACETAMIDO)BICYCLO[1.1.1]PENTAN-1-YL)-2-CYCLOBUTANE-1-CARBOXAMIDE DERIVATIVES AND RELATED COMPOUNDS AS ATF4 INHIBITORS FOR TREATING CANCER AND OTHER DISEASES
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The invention is directed to substituted bridged cycloalkane derivatives. Specifically, the invention is directed to compounds according to Formula (I) wherein X, a, b, C, D, L2,L3, Y1, Y2, R2, R4, R5, R6, z2, z4, z5, and z6 are as defined herein, and salts thereof. The invention is further directed to pharmaceutical compositions comprising a compound of the invention. The invention is still further directed to compounds for use in methods of inhibiting the ATF4 (activating transcription factor 4) pathway and treatment of disorders associated therewith, such as e.g. cancer, neurodegenerative diseases and many other diseases, using a compound of the invention or a pharmaceutical composition comprising a compound of the invention. Preferred compounds of the invention are N-(3-(2-(4-chlorophenoxy) acetamido)bicyclo[1.1.1]pentan-l-yl)-2-cyclobutane-l-carboxamide derivatives and related compounds.
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Page/Page column 98
(2019/01/21)
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- Novel impurity of tadalafil medicine, and preparation method and application of novel impurity
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The invention provides a compound, and a preparation method and application of the compound. The compound has a structure represented by a formula 2. According to the invention, when the compound is adopted as a standard substance or a reference substance, the compound can be effectively used for quality control of tadalafil bulk drugs and preparation products.
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Paragraph 0011; 0077-0078
(2018/04/01)
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- Isopropyl 2-ethoxyacetate—an efficient acylating agent for lipase-catalyzed kinetic resolution of amines in batch and continuous-flow modes
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Productivity [conversion (c) and specific reaction rate (rbatchor rflow)] and enantiomer selectivity [enantiomeric ratio (E) and enantiomeric excess (ee) of the products] of ethyl and isopropyl esters of acetic, 2-methoxyacetic and 2-ethoxyacetic acids as acylating agents were compared in the N-acylation of (±)-1-phenylethanamine rac-1 catalyzed by variously immobilized forms of Candida antarctica lipase B (CaLB) using shake flasks and continuous-flow reactors. The effect of the temperature in the 0–80 °C range on productivity and enantiomer selectivity in KRs of rac-1 was investigated with the isopropyl esters in continuous-flow mode using CaLB-filled minireactors. Isopropyl 2-ethoxyacetate surpassed the performance of ethyl 2-methoxyacetate in terms of both productivity (1.9–2.9 times higher rate in batch mode) and enantiomeric selectivity (ee(R)-amide>99.9% compared to 99.8%) providing at 40 °C high volumetric productivity (2.22 kg L?1h?1), specific reaction rate and enantiomeric excess (rflow=783 μmol min?1g?1, ee(R)-2c>99.9%).
- Oláh, Márk,Boros, Zoltán,Hornyánszky, Gábor,Poppe, László
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p. 7249 - 7255
(2016/10/26)
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- Larvicidal activity and click synthesis of 2-alkoxyl-2-(1,2,3-triazole-1- yl)acetamide library
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Heterogeneous copper-in-charcoal-catalyzed click synthesis in 96-well polypropylene filter plates is an efficient method for the rapid generation of sufficient pure 2-alkoxyl-2-(1,2,3-triazole-1-yl) acetamide derivatives library by simple filtration, which directly assay the products for larvicidal activity against mosquitoes. In this procedure, copper nanoparticles on charcoal were arrayed into each well on a 96-well plate, reagents were delivered using a pipette gun, and a constant temperature shaker bath was used to complete the click reaction in 24-72 hours under temperature-controlled conditions. The results of bioassays indicated that the target compounds possessed excellent larvacidal activities against mosquitoes. In particular, the larvacidal activities against mosquitoes of compounds 8[2,3] and 8[7,1] at 2g.mL-1 were 100% and 73%, respectively.
- Su, Na-Na,Xiong, Li-Xia,Yu, Shu-Jing,Zhang, Xiao,Cui, Can,Li, Zheng-Ming,Zhao, Wei-Guang
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p. 484 - 493
(2013/07/28)
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- Asymmetric hydrogenation of α- Or β-acyloxy α,β- unsaturated phosphonates catalyzed by a Rh(i) complex of monodentate phosphoramidite
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The Rh(i) complex of a monodentate phosphoramidite bearing a primary amine moiety (DpenPhos) has been disclosed to be highly efficient for the asymmetric hydrogenation of a variety of α- or β-acyloxy α,β- unsaturated phosphonates, providing the corresponding biologically important chiral α- or β-hydroxy phosphonic acid derivatives with excellent enantioselectivities (90->99% ee).
- Zhang, Jinzhu,Dong, Kaiwu,Wang, Zheng,Ding, Kuiling
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supporting information; scheme or table
p. 1598 - 1601
(2012/03/22)
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- Chromium(VI) oxide oxidation of non-ethoxylated and ethoxylated alcohols for determination by electrospray ionization mass spectrometry
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A new derivatization procedure to increase the sensitivity of electrospray ionization mass spectrometry (ESI-MS) to non-ethoxylated and ethoxylated alcohols was investigated. The analytes were oxidized with chromium(VI) oxide and the resulting carboxylic and ethoxy-carboxylic acids were isolated by extraction with ethyl acetate; the extracts were alkalinized and infused into the ESI-MS system working in the negative-ion mode. The yields of the combined oxidation-extraction were ca. 100% for non-ethoxylated fatty alcohols dissolved in acetone and they decreased moderately in samples containing increasing amounts of water (e.g., a 75% yield was obtained with 50% water). Ethoxylated alcohols with more than two ethylene oxide units resulted in yields of ca. 60%. Low limits of detection (LODs) were obtained when the procedure was applied to the analysis of body- care products and cosmetics containing fatty alcohols, e.g., in a varicose-vein cream, the LODs were 25 μ cetyl alcohol and 7.5 μ stearyl alcohol (detected as palmitic acid and stearic acid, respectively) per gram of sample. High molecular mass alcohols were also detected in seawater after pre- concentration by solid-phase extraction. Thus, the proposed method is particularly valuable for use in industrial samples having complex matrices and in environmental samples and it is competitive with other methods for the analysis of trace amounts of fatty alcohols.
- Beneito-Cambra, Miriam,Bernabe-Zafon, Virginia,Simo-Alfonso, Ernesto F.,Ramis-Ramos, Guillermo
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experimental part
p. 2093 - 2100
(2011/11/06)
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- 2-Arylbenzoxazoles as CETP inhibitors: Substitution and modification of the α-alkoxyamide moiety
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The development of a series of 2-arylbenzoxazole α-alkoxyamide and β-alkoxyamine inhibitors of cholesteryl ester transfer protein (CETP) is described. Highly fluorinated α-alkoxyamides proved to be potent inhibitors of CETP in vitro, and the highly fluorinated 2-arylbenzoxazole β-alkoxyamine 4 showed a desirable combination of in vitro potency (IC50 = 151 nM) and oral bioavailability in the mouse.
- Hunt, Julianne A.,Gonzalez, Silvia,Kallashi, Florida,Hammond, Milton L.,Pivnichny, James V.,Tong, Xinchun,Xu, Suoyu S.,Anderson, Matt S.,Chen, Ying,Eveland, Suzanne S.,Guo, Qiu,Hyland, Sheryl A.,Milot, Denise P.,Sparrow, Carl P.,Wright, Samuel D.,Sinclair, Peter J.
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scheme or table
p. 1019 - 1022
(2010/06/14)
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- Kinetics and mechanism of the oxidation of ethyl glycol, D-mannitol and D-sorbitol by hexacyanoferrate(III) ion in aqueous alkaline medium
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The rate of oxidation of ethyl glycol, D-mannitoI and D-sorbitol by hexacyanoferrate(III) ion in aqueous alkaline medium is directly proportional to the organic substrate and hydroxide ion concentrations. The dependence of rate on hexa-cyanoferrate(III) ion is nearly first order at lower concentrations and tends towards zero order at higher concentrations. A probable reaction mechanism has been suggested.
- Singh,Verma,Gupta, Arti,Mittal, Anjali
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p. 392 - 394
(2007/10/03)
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- SAR in the alkoxy lactone series: The discovery of DFP, a potent and orally active COX-2 inhibitor
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Extensive SAR has been established in the alkoxy lactone series and this has lead to the discovery of DFP (5,5-dimethyl-3-(2-propoxy)-4- methanesulfonylphenyl)-2(5H)-furanone), a potent COX-2 inhibitor exhibiting in vivo efficacy in all models studied.
- Leblanc,Roy,Boyce,Brideau,Chan,Charleson,Gordon,Grimm,Guay,Leger,Li,Riendeau,Visco,Wang,Webb,Xu,Prasit
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p. 2207 - 2212
(2007/10/03)
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- Preparation of naphthoquinone derivatives from plumbagin and their ichthyotoxicity
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Various naphthoquinone derivatives were prepared from a natural product, 5-hydroxy-2-methyl-1,4-naphthoquinone (plumbagin); these were mostly substituted at C-3 through carbon-carbon bond formation mediated by a metal- based oxidant such as lead tetraacetate in the presence of various carboxylic acids. The halogenated compounds showed stronger ichthyotoxicity than plumbagin, but other derivatives were less active.
- Ogihara, Kazuhito,Yamashiro, Rieko,Higa, Matsutake,Yogi, Seiichi
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p. 437 - 445
(2007/10/03)
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- Lithiomethyl ethyl ether from chloromethyl ethyl ether via a DTBB-catalysed lithiation
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The reaction of equimolar amounts of chloromethyl ethyl ether (1) and a carbonyl compound [Bu(n)CHO, Bu(t)CHO, PhCHO, Pr(i)2CO, Bu(t)2CO, (CH2)4CO, 2-cyclohexenone, PhCOMe] with an excess of lithium powder (1:7 molar ratio) and a catalytic amount of DTBB (5 mol%) in THF at 0°C (Method A) leads, after hydrolysis, to the corresponding hydroxyethers 2. The reaction can be also carried out in a two-step process: tandem lithiation at -90°C and reaction with the electrophile [Bu(n)CHO,(CH2)4CO, PhCOMe, PhMe2SiCl, CO2, PhCN, PhCONMe2, CyNCO, PhN=CHPh] at -90 to -60°C (Method B).
- Guijarro, Albert,Mancheno, Balbino,Ortiz, Javier,Yus, Miguel
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p. 1643 - 1650
(2007/10/03)
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- An unusual pathway of the oxidation of diethyl ether by bismuth(V) derivatives
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Di(tert-butylperoxy)triphenylbismuth and the triphenylbismuth-tert-butyl hydroperoxide system transform diethyl ether into ethoxyacetic aldehyde.The latter undergoes further conversions under these reaction conditions to give the corresponding hydroperoxide, ethoxyacetic acid, and bismuth(III) acylates. - Key words: diethyl ether, ethoxyacetic aldehyde, triphenylbismuth, tert-butyl hydroperoxide, oxidation.
- Dodonov, V. A.,Zinov'eva, T. I.,Dolganova, N. V.
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p. 764 - 765
(2007/10/02)
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- ENZYLATICALLY CLEAVABLE ALKOXYCARBONYL ETHOXYMETHYL ESTERS FOR REVERSIBLE BLOCKING OF CARBOXYL GROUPS
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By O-alkylation carboxylic acids with α-bromo-α-ethoxy acetates new alkoxycarbonyl ethoxymethyl esters (ACEM esters) were synthesised in a simple route.The ACEM blocking group can be casily cleft by esterases.
- Klemm, D.,Geschwend, G.
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p. 2337 - 2348
(2007/10/02)
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- Novel class of acyl-derivatives of carnitine process for preparing same and therapeutic use thereof
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A novel class of acyl-derivatives of carnitine is disclosed wherein the acyl radical is either the radical of unsaturated organic acids (typically, acrylic acid) or the radical of saturated organic acids substituted with tert-alkyl, cycloalkyl, cycloalkenyl, alkoxyl, heterocyclic and carboalkoxylradicals, or with aldehyde or hydroxy groups. These acyl-derivatives of carnitine are useful therapeutical agents in the treatment of cardiac disorders, hyperlipidaemias and hyperlipoproteinaemias.
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- Hydrocarbonylation of ethyl orthoformate in the presence of rhodium catalysts
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The reaction of ethyl orthoformate with a mixture of CO and H2 (P 8 MPa) in the presence of various rhodium carbonyl catalysts with and without iodide promoters at temperatures of 150-170 deg C has been studied.The -/CH3I systems mainly catalyze the hydrogenation of ethyl orthoformate to diethoxymethane without any subsequent hydrogenation to methyl derivatives and methane.Carbonylation and hydrocarbonylation products of the ethyl moiety, i.e. ethyl propionate and 1,1-diethoxypropane together with diethyl carbonate coming from carbonylation of the ethoxy group, are produced, with a maximum selectivity of 12percent.Chlorocarbonylrhodium systems without iodide promoters are active in the hydrogenation and hydrocarbonylation of the substrate, whereas carbonylrhodium derivatives without halide ligands and promoters only catalyze the hydrogenation to diethoxymethane.IR spectroscopic studies show that the rhodium species produced under the reaction conditions are in all cases anionic halocarbonyl or carbonyl complexes, and the course of the reaction seems to depend on the hydrido character of the parent derivative.
- Raspolli Galletti, A.M.,Braca, G.,Sbrana, G.
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p. 221 - 232
(2007/10/02)
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- Photolysis of Alkoxyacetic Acids in the presence of Mercury(II) Oxide and Iodine
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Homolytic decarboxylation of a series of alkoxyacetic acids has furnished alkoxyalkyl alkoxyacetates when no substituents were present at the 2-position.Electron donating and withdrawing 2-substituents, with the exception of trichloromethyl, afforded products due to fragmentation of the alkoxyacetic acids.The reaction pathway is rationalised on the basis of the reactivity of the alkoxyalkyl iodide intermediates.
- Glover, Stephen A.,Golding, Stephen L.,Goosen, Andre,McCleland, Cedric W.
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p. 2479 - 2483
(2007/10/02)
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- 3-(3,4-Epoxy-4-methylcyclohexyl)butyl esters
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3-(3,4-Epoxy-4-methylcyclohexyl)butyl esters form a new class of compounds exhibiting fungicidal activity and plant growth regulant activity. In fungicide tests, the compounds of this invention prove effective against Fusarium oxysporium, Pythium debaryanum, Rhizoctonia solani and Sclerotium rolfsii. In herbicide tests, post-emergent application of the compounds of this invention provides plant growth regulant action, such as cotton defoliation and plant growth retardation activity.
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