• Title/Summary/Keyword: Ring-opening

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A Unique Function of Reaction Path (II). Applications to Thermal Electrocyclic Reactions (반응 경로의 일의적 함수 (제 2 보). Thermal Electrocyclic Reaction 에 대한 응용)

  • Kim, Ho-Jing;Jang, Hyo-Weon
    • Journal of the Korean Chemical Society
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    • v.32 no.2
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    • pp.103-112
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    • 1988
  • For two possible paths of thermal ring opening reactions, the approximate reaction path functions, their norms and the approximate reaction path average energies are computed and compared. Illustrated examples clearly justify the postulate that the path with larger norm and lower average energy has lower barrier height than the other.

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The Organization of Nanoporous Structure Using Controlled Micelle Size from MPEG-b-PDLLA Block Copolymers

  • Chang, Jeong-Ho;Kim, Kyung-Ja;Shin, Young-Kook
    • Bulletin of the Korean Chemical Society
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    • v.25 no.3
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    • pp.351-356
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    • 2004
  • Selected MPEG-b-PDLLA block copolymers have been synthesized by ring-opening polymerization with systematic variation of the chain lengths of the resident hydrophilic and hydrophobic blocks. The size and shape of the micelles that spontaneously form in solution are then controlled by the characteristics of the block copolymer template. All the materials prepared in this study showed the tunable pore size of 20-80 ${\AA}$ with the increase of hydrophobic chain lengths and up to 660 $m^2$/g of specific surface area. The formation mechanism of these nanoporous structures obtained by controlling the micelle size has been confirmed using both liquid and solid state $^{13}C\;and\;^{29}Si$ NMR techniques. This work verifies the formation mechanism of nanoporous structures in which the pore size and wall thickness are closely dependent on the size of hydrophobic cores and hydrophilic shells of the block copolymer templates.

Synthesis of Chiral Intermediates Catalyzed by New Chiral Polymeric (Salen) Cobalt Complexes Bearing Lewis Acidic Metal Halides

  • Lee, Kwang-Yeon;Kawthekar, Rahul B.;Kim, Geon-Joong
    • Bulletin of the Korean Chemical Society
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    • v.28 no.9
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    • pp.1553-1561
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    • 2007
  • The new type of heterometallic chiral polymer salen complexes have been synthesized and it has been found that group 13 metal salts (AlCl3, GaCl3 and InCl3) combined to cobalt salen unit played the crucial role in the asymmetric kinetic resolution of racemic epoxides. Polymeric salen catalysts showed very high reactivity and enantioselectivity for the asymmetric ring opening of terminal epoxide with diverse nucleophiles. They provide the enantiopure useful chiral intermediates such as chiral terminal epoxides and α -aryloxy alcohols in one-step process. An efficient methodology for providing very high enantioselectivity can be achieved in the synthesis of valuable chiral building blocks via our catalytic system by combination of various asymmetric ring opening reactions.

Synthesis of New Bimetallic Chiral Salen Catalyst Bearing Co(BF4)2 Salt and Its Application in Asymmetric Ring Opening of Epoxide

  • Kim, Yong-Suk;Lee, Choong-Young;Kim, Geon-Joong
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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    • pp.2973-2979
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    • 2010
  • The newly synthesized homogeneous chiral Co(III) salen complexes were anchored non-covalently on the acidic sites of mesoporous Al-SBA-15. The Bronsted and Lewis acidic sites are attributed to the immobilization of fluorine functionalized chiral salen complexes on the supports. XRD, BET, TEM, FT-IR and ESCA (XPS) analyses were performed to characterize the property of support, and the structure of new homogeneous and heterogeneous chiral Co salen catalyst. The homogeneous and heterogeneous catalysts could be applied in asymmetric ring opening of epichlorohydrine (ECH) by water. They showed very high enantioselectivity and a good yield up to 99% in the catalytic synthesis of optically active products.

Asymmetric Ring Opening of Terminal Epoxides Catalyzed by Chiral Co(III)-BF3 Salen Complex Immobilized on SBA-16

  • Kim, Yong-Suk;Lee, Choong-Young;Kim, Geon-Joong
    • Bulletin of the Korean Chemical Society
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    • v.30 no.8
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    • pp.1771-1777
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    • 2009
  • The homogeneous B$F_3$ containing chiral Co(III) salen complexes were anchored non-covalently on the surfaces of mesoporous SBA-16 silica containing aluminum species. The Brönsted and Lewis acidic sites are attributed to the immobilization of fluorine functionalized chiral salen complexes on the supports. The FT-IR, UV, ESCA, and NMR analyses were performed to determine the structure of synthesized chiral salen catalysts. These heterogeneous catalysts could be applied in asymmetric ring opening of terminal epoxides by water and phenol derivatives. They showed very high enantioselectivity and yield more than 98% in the catalytic synthesis of optically active products.

Selective Ring-opening Fluorination of Epoxide: An Efficient Synthesis of 2'-C-Fluoro-2'-C-methyl Carbocyclic Nucleosides

  • Liu, Lian-Jin;Kim, Si-Wouk;Lee, Won-Jae;Hong, Joon-Hee
    • Bulletin of the Korean Chemical Society
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    • v.30 no.12
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    • pp.2989-2992
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    • 2009
  • An efficient synthetic route of novel 2′(${\alpha}$)-C-fluoro-2′(${\beta}$)-C-methyl carbocyclic nucleoside analogues is described. The key fluorinated intermediate 7 was prepared from the epoxide intermediate 5 via selective ring-opening of epoxide. Coupling of 7 with nucleosidic bases under the Mitsunobu reactions followed by deprotection afforded the target carbocyclic nucleoside analogues. The synthesized compounds were evaluated as inhibitors of the hepatitis C virus (HCV) in Huh-7 cell line in vitro.

Formal Synthesis of Sex Pheromone of Gypsy Moth (+)-Disparlure from L-(+)-Tartaric Acid

  • Gi Baek Gwon;Hang Soo Kim;Jae Won Park;Jong Soo Choi;Kyung Oh Doh;Kyung Jin Kim;Young Bae, Seu
    • Journal of the Korean Chemical Society
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    • v.68 no.3
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    • pp.131-134
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    • 2024
  • A simple strategy for the formal synthesis of the sex pheromone of gypsy moth (+)-disparlure from L-(+)-tartaric acid is described herein. The key steps include the mono-esterification and regioselective ring-opening of an epoxide using a Grignard reagent. The strategy of conferring asymmetry using 2-butanone enables mono-esterification in high yield and reduces the number of steps. Subsequently, (+)-disparlure is synthesized via the regioselective ring opening of the epoxide.

Study of HOMO and LUMO Energy Levels for Spirolactam Ring Moiety Using Electrochemical Approach

  • Kim, Hyungjoo;Lee, Sehoon;Son, Young-A
    • Textile Coloration and Finishing
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    • v.25 no.2
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    • pp.83-88
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    • 2013
  • Rhodamine dyes have been studied in various scientific areas due to their excellent photophysical properties. In particular, these rhodamine dyes are one of the most famous fluorophores as signal unit in chemosensor study. This is related to spirolactam ring system in rhodamine dyes. When the spirolactam ring is closed, there is nonfluorescence and colorless. Whereas, ring-opening of the corresponding spirolactam induces strong fluorescence and color. These absorption and emission changes are related to structural changes as well as electron energy potential levels such as HOMO and LUMO values. In this study, two different structures of rhodamine 6G hydrazide depending on the spirolactam ring system were investigated using absorption measurement, electrochemical measurement and computational calculations.

Ring Oxpening Polymerization of D,L-Lactide on Magnetite Nanoparticles

  • Tian Jing;Feng Ya-Kai;Xu Yong-Shen
    • Macromolecular Research
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    • v.14 no.2
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    • pp.209-213
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    • 2006
  • The ring-opening polymerization of D,L-lactide initiated by tin(II) 2-ethylhexanoate $(Sn(Oct)_2)$ on the surface-initiated magnetite $(Fe_{3}O_4)$ nanoparticles was performed at $130^{\circ}C$. The effects of the polymer molar mass and concentration on the amount of surface polymer were investigated. The number average molecular weights, $M_n$, obtained by both NMR and GPC methods fit well within the accuracy of the applied methods and ranged from 1,100 to $4,040g\;mol^{-1}$. A surface functionalization density of up to 625 initiation sites per particle was obtained. The composition of various core-shell particles was determined by TGA, with results indicating magnetite $(Fe_{3}O_4)$ contents, ${\mu}m$, between 17 and 59 wt%. Under the influence of a magnetic field, the heating generated by superparamagnetic core-shell particles suspended in toluene presented guidelines for an optimization of magnetic particle systems with respect to an application for hyperthermia.