• 제목/요약/키워드: Reductive coupling

검색결과 17건 처리시간 0.041초

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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    • 제32권11호
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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.

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

  • 김병효;최용락;김대호;한영필;백운필;전영무
    • 전기화학회지
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    • 제2권4호
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    • pp.209-212
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    • 1999
  • H-형의 분리 셀을 사용하여 중성 및 실온의 온화한 조건에서 조절 전위법 음전극 반응에 의한 nitroarene화합물들의 환원 짝지음 반응으로 높은 수율의 azobenzene유도체를 합성하였다. Pb또는 Pt cathode와 Pt anode를 사용하여 메탄을 용액 하에서 cyclic voltammetry에 근거하여 각 반응의 최적의 반응 조건을 결정한 후 반응을 실행하였으며, 대부분의 경우 환원 짝지음 반응은 치환기의 성질과 위치에 영향을 받지 않고 높은 수율로 성공적인 결과를 얻을 수 있었다.

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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    • 제27권11호
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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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    • 제30권2호
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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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    • 한국환경농학회 2011년도 30주년 정기총회 및 국제심포지엄
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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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