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Abstract: This study investigates the potential application of an efficient, easily recoverable and reusable KCC-1 nanoparticle-supported Salen/Ru(II) catalyst in the synthesis of 2-oxazolidinones from CO2, and propargylic amines. The KCC-1/Salen/Ru(II) NPs were thoroughly characterized by using TEM, SEM, TGA, FT-IR, ICP-MS, and BET. This observation was exploited in the direct and selective chemical fixation of CO2, affording high degrees of CO2 capture and conversion. The recycled catalyst has been analyzed by ICP-MS showing only minor changes in the morphology after the reaction, thus confirming the robustness of the catalyst.

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The reaction of propargylic amines and CO2 can provide high-value-added chemical products. However, most of catalysts in such reactions employ noble metals to obtain high yield, and it is important to seek eco-friendly noble-metal-free MOFs catalysts. Here, a giant and lantern-like [Zn116] nanocage in zinc-tetrazole 3D framework [Zn22(Trz)8(OH)12(H2O)9?8 H2O]n Trz=(C4N12O)4? (1) was obtained and structurally characterized. It consists of six [Zn14O21] clusters and eight [Zn4O4] clusters. To our knowledge, this is the highest-nuclearity nanocages constructed by Zn-clusters as building blocks to date. Importantly, catalytic investigations reveal that 1 can efficiently catalyze the cycloaddition of propargylic amines with CO2, exclusively affording various 2-oxazolidinones under mild conditions. It is the first eco-friendly noble-metal-free MOFs catalyst for the cyclization of propargylic amines with CO2. DFT calculations uncover that ZnII ions can efficiently activate both C?C bonds of propargylic amines and CO2 by coordination interaction. NMR and FTIR spectroscopy further prove that Zn-clusters play an important role in activating C?C bonds of propargylic amines. Furthermore, the electronic properties of related reactants, intermediates and products can help to understand the basic reaction mechanism and crucial role of catalyst 1.

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Compounds represented by the general formula (I): wherein each symbol is as defined in the description [with the proviso that 9-chloro-7-(1,1-dimethylethyl)-2,3,4,5-tetrahydro-1,4-benz-oxazepine and N-[[(5S)-2-oxo-3-(2,3,4,5-tetrahydro-1,4-benz-oxazepin-7-yl)-5-oxazolidinyl]methyl]acetamide are excluded], salts of the same, and prodrugs thereof have selective activation effect on serotonin 5-HT2C receptor and are useful as preventive and therapeutic agents for lower urinary tract diseases, obesity, and/or pelvic organ prolapse.

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The synthesis and biological activity of (1R,5S,6S)-2-[(3S,5S)-5-substituted pyrrolidin-3-ylthio]-6-[(1R)-1-hydroxyethyl]-1-methylcarbapen-2-em-3-carboxylic acids are described. These compounds exhibit potent antibacterial activity against a wide range of both Gram-positive and Gram-negative bacteria including Pseudomonas aeruginosa. Of these new carbapenems, (1R,5S,6S)-2-[(3S,5S)-5-sulfamoylaminomethyl pyrrolidin-3-ylthio]-6-[(1R)-1-hydroxyethyl]-1-methylcarbapen-2-em-3-carboxylic acid (S-4661) showed the most potent and well balanced activity and was selected as a candidate for further evaluation.

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Decarboxylative Csp3-N coupling reactions have been developed through electrochemical oxidation of amino acids. The reaction proceeds via anodic oxidative decarboxylation of carboxylic acids to form stabilized carbocations, which are trapped by azoles or amides to construct C-N bonds. This method avoids the preactivation of carboxylic acids and the use of expensive transition-metals and external chemical oxidants.

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We have shown that sulfuryl chloride is an efficient reagent for the conversion of 2-oxazolidinone into the dichloro derivative, N-acetyl-4,5- dichloro-2-oxazolidinone. Subsequent Zn/AcOH reductive dehalogenation of this trans-dichloride gives N-acetyl-2-oxazolone. The dichloride was previously reported as an undesired side product in the preparation of N-acetyl-2-oxazolone from the monochloro oxazolidinone. In our hands, the dichloride is a key intermediate in a new synthesis of 2-oxazolone, that avoids the use of chlorine gas. Georg Thieme Verlag Stuttgart.

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Quantum dot (QD) nanoparticles (NPs) are increasingly used as highly valuable fluorescent biomarkers and as sensitive (bio)chemical probes. Interestingly, if certain metal impurities are incorporated during the NPs synthesis, phosphorescent QDs with analytical potential can be obtained.We report here the synthesis of colloidal manganese-doped ZnS nanoparticles which have been surface-modified with l-cysteine that exhibit an intense room temperature phosphorescence (RTP) emission in aqueous media even in the presence of dissolved oxygen (i.e. sample deoxygenation is not needed). An exhaustive RTP photoluminescent and morphological characterization of the synthesized QDs and their potential for development of phosphorescent analytical methodologies is described. Application to analytical control of acetone (” model analyte” from the ketones family) in water and urine samples is carried out by measuring the QDs phosphorescence quenching rate.The observed results showed a high selectivity of Mn2+-doped ZnS QDs towards acetone. The linear range of the developed methodology turned out to be at least up to 600mgL-1 with a detection limit (DL) for acetone dissolved in aqueous medium of 0.2mgL-1. The developed methodology was finally applied for acetone determination in different spiked water and urine samples, and the recoveries fall in the range of 93-107%.

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A bismuth(III) triflate catalyzed three-component synthesis of alpha-substituted amides starting from amides, aldehydes, and (hetero)arenes is reported. The reaction has a broad substrate scope, encompassing formaldehyde as well as aryl and alkyl aldehydes. Low catalyst loadings are required, and water is formed as the only side product. The scope and limitation of this method will be discussed.

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Reaction between secondary amines and vinyl triflates of alpha-keto esters and imides under solvent-free condition provides a ready access to alpha,beta-diamino carboxylates.

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