• Title/Summary/Keyword: Reductive ring-opening

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Density Functional Studies of Ring-Opening Reactions of Li+-(ethylene carbonate) and Li+-(vinylene carbonate)

  • Han, Young-Kyu;Lee, Sang-Uck
    • Bulletin of the Korean Chemical Society
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    • v.26 no.1
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    • pp.43-46
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    • 2005
  • Reaction energies were determined for reductive ring-opening reactions of Li$^+$-coordinated ethylene carbonate (EC) and vinylene carbonate (VC) by a density functional method. We have also explored the ring-opening of Li$^+$-EC and Li$^+$-VC by reaction with a nucleophile (CH$_3$O$^-$.) thermodynamically. Our thermodynamic calculations led us to conclude that the possible reaction products are CH$_3$OCH$_2$CH$_2$OCO$_2$Li (O$_2$-C$_3$ cleavage) for Li$^+$-EC +CH$_3$O$^-$., and CH$_3$OCHCHOCO$_2$Li (O$_2$-C$_3$ cleavage) and CH$_3$OCO$_2$CHCHOLi (C$_1$-O$_2$ cleavage) for Li$^+$-VC +CH$_3$O$^-$.. The opening of VC would occur at the C$_1$-O$_2$ side by a kinetic reason, although the opening at the O$_2$-C$_3$ side is more favorable thermodynamically.

Formation of Methyl 2${\beta},\;3{\beta}$-Epoxy-23-hydroxyurs-12-en-28-oate from Asiaticoside and Its Reductive Epoxide Ring Opening Reaction (아시아티코사이드로부터 메칠 2${\beta},\;3{\beta}$-에폭시-23- 히드록시우르스-12-엔-28-오애이트의 합성 및 이의 환원적 에폭시환 개열반응)

  • Jew, Sang-Sup;Lim, Doo-Yeon;Seo, Sung-Ki;Nam, Tae-Gyu;Park, Hyeung-Geun;Kim, Hee-Doo;Kim, Chang-Min;Lee, Min-Hee;Paik, Hyeung-Geun;Lee, Min-Jung;Jung, Young-Hoon
    • YAKHAK HOEJI
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    • v.42 no.5
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    • pp.500-506
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    • 1998
  • Steroidal 2${\beta},\;3{\beta}$--epoxy compound was prepared from asiaticoside via six steps and reduced regioselectively with lithium aluminum hydride. Epoxide ring opening furnished 9 as a sole product at reflux condition through axial hydride attack at C-3.

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Polymerization of Hydrosilanes and Vinyl Monomers in the Presence of Transition Metal Complex

  • Kim, Myoung-Hee;Lee, Jun;Cha, Hyo Chang;Shin, Joong-Hyeok;Woo, Hee-Gweon
    • Journal of Integrative Natural Science
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    • v.2 no.1
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    • pp.18-23
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    • 2009
  • This minireview provides the chosen examples of our recent discoveries in the polymerization of hydrosilanes, dihydrosilole, lactones, and vinyl derivatives using various catalysts. Hydrosilanes and lactones copolymerize to give poly(lactone-co-silane)s with $Cp_2MCl_2$/Red-Al (M = Ti, Zr, Hf) catalyst. Hydrosilanes (including dihydrosilole) reduce noble metal complexes (e.g., $AgNO_3$, $Ag_2SO_4$, $HAuCl_4$, $H_2PtCl_6$) to give nanoparticles along with silicon polymers such as polysilanes, polysilole, polysiloxanes (and silicas) depending on the reaction conditions. Interestingly, phenylsilane dehydrocoupled to polyphenylsilane in the inert nitrogen atmosphere while phenylsilane dehydrocoupled to silica in the ambient air atmosphere. $Cp_2M/CX_4$ (M = Fe, Co, Ni; X = Cl, Br, I) combination initiate the polymerization of vinyl monomers. In the photopolymerization of vinyl monomers using $Cp_2M/CCl_4$ (M = Fe, Co, Ni), the photopolymerization of MMA initiated by $Cp_2M/CCl_4$ (M = Fe, Co, Ni) shows while the polymerization yield decreases in the order $Cp_2Fe$ > $Cp_2Ni$ > $Cp_2Co$, the molecular weight decreases in the order $Cp_2Co$ > $Cp_2Ni$ > $Cp_2Fe$. For the photohomopolymerization and photocopolymerization of MA and AA, the similar trends were observed. The photopolymerizations are not living. Many exciting possibilities remain to be examined and some of them are demonstrated in the body of the minireview.

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