• Title/Summary/Keyword: Reductive coupling

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Mechanistic Study of Half-titanocene-based Reductive Pinacol Coupling Reaction

  • Kim, Young-Jo;Do, Young-Kyu;Park, Sung-Jin
    • Bulletin of the Korean Chemical Society
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    • v.32 no.11
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    • pp.3973-3978
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    • 2011
  • The reductive pinacol coupling reaction of aldehydes or ketones creating a new C-C bond has been a major tool to produce 1,2-diol compounds. The reaction mechanism is known to be composed of sequential three steps (activation, coupling, and dissociation). In this work, we studied the dissociation step of half-titanocene-based catalytic systems. Cp and $Cp^*$ derivatives of the pinacolato-bridged dinuclear complex were synthesized and evaluated as possible models for intermediates from the coupling step. We monitored $^1H$-NMR spectra of the reaction between the metalla-pinacol intermediates and $D_2O$. New reaction routes of the dissociation step including oxo- and pinacolato-dibridged dinuclear complexes and oxo-bridged multinuclear complexes have been suggested.

Synthesis of Azobenzene Derivatives via Controlled Potential Cathodic Electrolysis (조절전위법 음전극 유기반응을 이용한 아조벤젠 유도체들의 합성)

  • Kim Byeong Hyo;Choi Yong Rack;Kim Dae Ho;Han Rongbi;Baik Woonphil;Jun Young Moo
    • Journal of the Korean Electrochemical Society
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    • v.2 no.4
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    • pp.209-212
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    • 1999
  • Using an H-type divided cell, reductive coupling reaction of nitroarene toward azobenzenes in a mild condition was successfully accomplished by the controlled potential cathodic electrolysis reaction. Optimum reaction potential of each reaction was determined based on cyclic voltammetric behavior in methanol solution at Pb or Pt cathode, and Pt anode. In most cases, reductive coupling reactions were successful with excellent yields regardless of the position and the character of the substituents.

Lanthanide-Oxalate Coordination Polymers Formed by Reductive Coupling of Carbon Dioxide to Oxalate: [Ln2(3,5-pdc)2(C2O4)(H2O)4]·2H2O (Ln = Eu, Sm, Ho, Dy; pdc = Pyridinedicarbox

  • Huh, Hyun-Sue;Lee, Soon W.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.11
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    • pp.1839-1843
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    • 2006
  • Hydrothermal reactions of $Ln(NO_3)_3{\cdot}5H_2O $ (Ln = Eu (1), Sm (2), Ho (3), Dy (4)) with 3,5-pyridinedicarboxylic acid (3,5-pdcH2) in the presence of 4,4'-bipyridine led to the formation of the 3-D Ln(III)-coordination polymers with a formula unit of $[Ln_2(3,5-pdc)_2(C_2O_4)(H_2O)_4]{\cdot}2H_2O$. These polymers contain a bridging oxalate ligand ($C_2O_4\;^2$). On the basis of GCMS study of the mother liquor remaining after the reaction, we proposed that the $C_2O_4\;^2$ formation proceeds in three steps: (1) Ln(III)-mediated decarboxylation of $3,5-pdcH_2$ to give $CO_2$, (2) the reduction of $CO_2$ to $CO_2\;^{\cdot}$ by the Ln(II) species, and (3) the reductive coupling of the two $CO_2\;^{\cdot}$ radicals to the oxalate ($C_2O_4\;^2$) ion. All polymers were structurally characterized by X-ray diffraction.

Platinum-Catalyzed Reductive Aldol and Michael Reactions

  • Lee, Ha-Rim;Jang, Min-Soo;Song, Young-Jin;Jang, Hye-Young
    • Bulletin of the Korean Chemical Society
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    • v.30 no.2
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    • pp.327-333
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    • 2009
  • For the Pt-catalyzed nucleophilic addition of enones, Pt complexes were employed in the presence of various phosphine ligands and $H_2\;(or\;Et_3SiH),$ affording inter- and intra-molecular coupling products in good to modest yield. Depending on reaction protocols, different phosphine ligands were required to optimize the conditions. In the aldol reaction, the Pt catalyst involving $P(2,4,6-(OMe)_3C_6H_2)3\;or\;P(p-OMeC_6H_4)_3$ was chosen. Michael reaction proceeds in good yields in the presence of $P(p-CF_3C_6H_4)_3$. Regarding the activity of the reductants, $H_2$ exhibited superior activity to $Et_3SiH$, resulting in a shorter reaction time and higher yield in the aldol and Michael reaction. In light of the deuterium labeling studies, the catalytic cycle including the hydrometalation of the enones by the platinum hydride species was proposed.

Anaerobic Degradation of Aromatic Compounds by Microorganisms in Paddy Field

  • Katayama, A.;Yoshida, N.;Shibata, A.;Baba, D.;Yang, S.;Li, Z.;Kim, H.;Zhang, C.;Suzuki, D.
    • 한국환경농학회:학술대회논문집
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    • 2011.07a
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    • pp.128-135
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    • 2011
  • Consortia demonstrated the high capacities of anaerobic degradation of various aromatic compounds, which were successfully enriched from gley paddy soils under different conditions. Phenol and cresol was decomposed anaerobically using nitrate, ferric oxide or sulfate as electron acceptors. Biphenyl was degraded to $CO_2$, especially without addition of external electron acceptor. Alkylphenols with middle length of alkyl chain, were co-metaboliocally degraded with the presence of hydroxylbenzoate as the co-substrate under nitrate reducing conditions. The microorganisms responsible for the anaerobic co-metabolism was Thauera sp. Reductive dechlorination activity was also observed for polychlorophenols, fthalide, polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins with the presence of lactate, formate or $H_2$ as electron donor. The fthalide dechlorinator was classified as Dehalobacter sp. Coupling of two physiologically-distinct anaerobic consortia, aromatic ring degrader and reductive dechlorinator, resulted in the mineralization of pentachlorophenol under anaerobic conditions. These results suggested that gley paddy soils harbored anaerobic microbial community with versatile capacity degrading aromatic compounds under anaerobic conditions.

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