• Title/Summary/Keyword: Asymmetric catalysis

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Chiral Mesoporous Silica for Asymmetric Metal-free Catalysis: Enhancement of Chirality thorough Confinement Space by Plug Effect

  • Jeong, Eun-Yeong;Im, Cheong-Rae;Park, Sang-Eon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.199-199
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    • 2011
  • The addition of a carbanion to ${\yen}{\acute{a}}{\yen}{\hat{a}}$-unsaturated carbonyl compounds is of importance in the C-C bond formation reactions for modern pharmaceuticals and organic synthesis. Recently, heterogeneous asymmetric catalysis became more attractive area of research because of the easy recovery and separation of the catalyst from the reaction system. Most of synthetic methods for heterogeneous catalysts were grafting or immobilization of homogeneous catalyst onto the solid supports. Trans-1,2-Diaminocyclohexane(DACH) and L-proline ligands have been enormously used as chiral ligands in several catalytic transformation under homogenous conditions. Our group prepared l-proline functionalized mesoporous silica was synthesized under acidic condition using a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer template (EO20PO70EO20, Pluronic P-123, BASF). Furthermore, we successfully directly synthesized trans-1,2 diaminocyclohexane functionalized mesoporous silica by using microwave method. The direct functionalization of chiral ligand into the framework of mesoporous materials is expected to be useful for the heterogeneous asymmetric catalysis. So, we adopt the direct synthesis of chiral ligand functionalized mesoporous silica by using thermal and microwave irradiation. Then, chiral ligand functionalized mesoporous silicas were applied to enantioselective asymmetric catalytic reactions.

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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.

Biomimetic Catalysis in Ionic Liquids: Markedly Enhanced Enantioselectivity in Amino Acid-Catalyzed Directed Asymmetric Aldol Reactions

  • Yun, Suk-Jin;Lee, Jae Kwan
    • Journal of Integrative Natural Science
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    • v.8 no.2
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    • pp.107-110
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    • 2015
  • Amino acid-catalyzed directed asymmetric aldol reactions showed enhanced enantioselectivity when conducted in ionic liquids. Optically active products were afforded in better yields (up to 23% higher) and enantiomeric excess (up to 21% higher) in ionic liquids than in conventional organic solvents.

Development of Ferrocene-Containing Metal Catalysts for Asymmetric Synthesis (페로센을 이용한 비대칭 유기합성용 금속 촉매의 개발)

  • Oh, Yunghee;Choi, Mi-Jin
    • Applied Chemistry for Engineering
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    • v.10 no.5
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    • pp.804-807
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    • 1999
  • New copper complexes with a ligand, L(L=N,N'-cyclohexane bis(ferrocenylmethylene)amine) which was obtained from ferrocene carboxaldehyde and 1,2-diaminocyclohexane with a mole ratio of 2:1, were prepared and characterized. Those were adapted to asymmetric catalysis. The copper(II) complexes do not work in cyclopropanation of styrene and ethyl diazoacetate but copper(I) complex catalyzes. The Cu(I)LOTf (OTf=trifluorometanesulfonate) shows a good regioselectivity giving high trans to cis ratio of up to 80:20.

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Non-Covalent Immobilization of Chiral (Salen) Complexes on HF-treated Mesoporous MFI-type Zeolite for Asymmetric Catalysis

  • Lee, Kwang-Yeon;Lee, Choong-Young;Kim, Geon-Joong
    • Bulletin of the Korean Chemical Society
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    • v.30 no.2
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    • pp.389-396
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    • 2009
  • MFI structural zeolite (ZSM-5 or Sililcalite) was treated with HF solution to introduce mesoporous channels in the microporous crystals. Inner mesopore size could be controlled from 2.5 to 3.5 nm by changing the concentration of HF solution. The pore structure of HF-treated MFI zeolite was studied by instrumental analysis. The active Co (III) salen complex monomers were successfully anchored non-covalently on the surfaces of mesoporous MFI-type zeolite. These heterogeneous catalysts could be applied in asymmetric ring opening of terminal epoxides by phenol derivatives. It showed very high enantioselectivity and yield up to 95% in the catalytic synthesis of optically active $\alpha$-aryloxy alcohol compounds.