• Title/Summary/Keyword: metal catalysis

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Dynamic Kinetic Resolutions and Asymmetric Transformations by Enzyme-Metal Combo Catalysis

  • Kim, Mahn-Joo;Ahn, Yang-Soo;Park, Jai-Wook
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.515-522
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    • 2005
  • Enzyme-metal combo catalysis is described as a useful methodology for the synthesis of optically active compounds. The key point of the method is the use of enzyme and metal in combination as the catalysts for the complete transformation of racemic substrates to single enantiomeric products through dynamic kinetic resolution (DKR). In this approach, enzyme acts as an enantioselective resolving catalyst and metal does as a racemizing catalyst for the efficient DKR. Three kinds of enzyme-metal combinations - lipase-ruthenium, subtilisin-ruthenium, and lipase-palladium –have been developed as the catalysts for the DKRs of racemic alcohols, esters, and amines. The scope of the combination catalysts can be extended to the asymmetric transformations of ketones, enol acetates, and ketoximes via the DKRs. In most cases studied, enzyme-metal combo catalysis provided enantiomerically-enriched products in high yields.

Construction of Strontium Titanate/Binary Metal Sulfide Heterojunction Photocatalysts for Enhanced Visible-Light-Driven Photocatalytic Activity

  • Yu, Yongwei;Yang, Qing;Ma, Jiangquan;Sun, Wenliang;Yin, Chong;Li, Xiazhang;Guo, Jun;Jiang, Qingyan;Lu, Zhiyuan
    • Nano
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    • v.13 no.11
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    • pp.1850130.1-1850130.12
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    • 2018
  • A novel strontium titanate/binary metal sulfide ($SrTiO_3/SnCoS_4$) heterostructure was synthesized by a simple two-step hydrothermal method. The visible-light-driven photocatalytic performance of $SrTiO_3/SnCoS_4$ composites was evaluated in the degradation of methyl orange (MO) under visible light irradiation. The photocatalytic performance of $SrTiO_3/SnCoS_4-5%$ is much higher than that of pure $SrTiO_3$, $SnCoS_4$, $SrTiO_3/SnS_2$ and $SrTiO_3/CoS_2$. The $SrTiO_3/SnCoS_4$ composite material with 5 wt.% of $SnCoS_4$ showed the highest photocatalytic efficiency for MO degradation, and the degradation rate could reach 95% after 140 min irradiation time. The enhanced photocatalytic activity was ascribed to not only the improvement of visible light absorption efficiency, but also the construction of a heterostructure which make it possible to effectively separate photoexcited electrons and holes in the two-phase interface.

Transition metal-mediated/catalyzed fluorination methodology developed in the 2000s

  • Bae, Dae Young;Lee, Eunsung
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.3 no.2
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    • pp.122-128
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    • 2017
  • In the 2000s, there has been a significant advance on carbon-fluorine (C-F) bond formation reactions via transition metal mediated or catalyzed methods. Of course, for the past 10 years, transition metal catalysis improves C-F bond formation in terms of practicality and even can be applied to C-18F bond formation reaction. In this mini-review, we summarize various transition metal mediated or catalyzed fluorination reactions, which were developed in the mid-2000s.

Development of Novel Pyrrolidine Organocatalyst

  • Im, Seol-Hui;Gang, Seong-Ho
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.198-198
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    • 2011
  • Organocatalysis is a relatively new and popular area within the field of chiral molecule synthesis. It is one of the main branches of enantioselective synthesis with enzymatic and organometallic catalysis. In recent years, immense high quality studies on catalysis by chiral secondary amines were reported. These progresses instantly led to different organocatalytic activation concepts, so thousands of researchers from academia and the chemical industry are currently involved in this field and new ideas, new approaches, and creative thinking have been rapidly emerged. Organocatalysts, some of which are natural products, appear to solve the problems of metal catalysts. Compared to metal-based catalysis, they have many advantages including savings in cost, time, and energy, easier experimental procedure, and reduction of chemical waste. These benefits originate from the following factors. First, organocatalysts are generally stable in oxygen and water in the atmosphere, there is no need for special equipments or experimental techniques to operate under anhydrous or anaerobic conditions. Second, organic reagents are naturally available from biological materials as single enantiomers that they are easy and cheap to prepare which makes them suitable for small-scale to industrial-scale reactions. Third, in terms of safety related catalysis, small organic molecules are non-toxic and environmentally friendly. Therefore, the purpose of this research is to develop novel synthetic methods and design for various organocatalyst. Furthermore, it is expected that these organocatalysts can be applied to a variety of asymmetric reactions and study the transition state of these reactions using a metal sulface. Here, we report the synthesis of unprecedented organocatalysts, proline and pyrrolidine derivatives with quaternary carbon center.

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Metal Ion Catalysis and Inhibition in Nucleophilic Substitution Reactions of 4-Nitrophenyl Nicotinate and Isonicotinate with Alkali Metal Ethoxides in Anhydrous Ethanol

  • Choi, Seo-Young;Hong, Yeon-Ju;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.32 no.6
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    • pp.1951-1956
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    • 2011
  • A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate 5 and isonicotinate 6 with alkali metal ethoxide EtOM (M = K, Na, and Li) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. Plots of pseudo-first-order rate constant $k_{obsd}$ vs. EtOM concentration exhibit upward curvature for the reactions of 5 and 6 with EtOK and EtONa but are almost linear for those with EtOLi. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has shown that $k_{EtOK}$ ${\geq}$ $k_{EtONa}$ > $k_{EtO^-}$ but $k_{EtOLi}$ < $k_{EtO^-}$. It has been concluded that $K^+$ and $Na^+$ ions catalyze the reactions by increasing the electrophilicity of the carbonyl carbon atom through formation of a 4-membered cyclic transition state $TS_3$ or $TS_4$. However, $M^+$ ion catalysis has been found to be much less significant for the reactions of 5 and 6 than for the corresponding reactions of 4-nitrophenyl picolinate 4, which was reported to proceed through a 5-membered cyclic transition state $TS_2$. Although 5 and 6 are significantly more reactive than 4-nitrophenyl benzoate 3, the reactions of 5 and 6 result in smaller $k_{EtOK}/k_{EtO^-}$ ratios than those of 3. The electron-withdrawing ability of the nitrogen atom in the acyl moiety of 5 and 6 has been suggested to be responsible for the increase in reactivity and the decrease in the $k_{EtOK}/k_{EtO^-}$ ratio.

Microwave Synthesis of a Porous Metal-Organic Framework, Nickel(II) Dihydroxyterephthalate and its Catalytic Properties in Oxidation of Cyclohexene

  • Lee, Ji-Sun;Halligudi, Shiva B.;Jang, Nak-Han;Hwang, Dong-Won;Chang, Jong-San;Hwang, Young-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.31 no.6
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    • pp.1489-1495
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    • 2010
  • A porous coordination solid of nickel(II) dihydroxyterephthalate has been synthesized by the microwave-assisted (MW) method. The synthesized nickel(II) dihyroxylterephthalate was designated by the general formula of [$Ni_2$(dhtp) $(H_2O)_2]{\cdot}8H_2O$ (where, dhtp = 2,5-dihydroxyterephthalate, denoted by Ni-DHTP). The effect of microwave-irradiation temperature and time of irradiation on the porosity and morphological changes in the solids have also been investigated. The catalytic performance of Ni-DHTP synthesized by MW method has been studied in the oxidation of cyclohexene with aqueous $H_2O_2$, which gave cyclohexene oxide as the primary product and 2-cyclohexene-1-ol as a major product.