Ni(uroporphyrin) | 84098-84-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: Ni(uroporphyrin)
• 英文别名: nickel(II)-uroporphyrin I
• CAS: 84098-84-0
• 化学式: C₄₀H₃₆N₄NiO₁₆
• 分子量: 887.433
• InChiKey: GIAVYXHKVPJKER-MXOXSBADSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  nickel(II) sulphate 、 uroporphyrin I 在 recombinant Archaeoglobus fulgidus nickel chelatase CfbA, complex with Co(II) (1:1) 、 sodium chloride 作用下， 以 aq. buffer 为溶剂， 生成 Ni(uroporphyrin)
  参考文献：
  名称：

  CfbA promotes insertion of cobalt and nickel into ruffled tetrapyrrolesin vitro

  摘要：

  CfbA将一种不稳定的金属插入到一个皱褶的四吡咯环中。

  DOI：

  10.1039/c9dt03601f

文献信息

• Catalytic diversification upon metal scavenging in a prebiotic model for formation of tetrapyrrole macrocycles
  作者：Ana R. M. Soares、Dana R. Anderson、Vanampally Chandrashaker、Jonathan S. Lindsey

  DOI：10.1039/c3nj00498h

  日期：——

  A prebiotic model for the formation of tetrapyrrole macrocycles was examined in aqueous solution containing representative Earth-available metals [Mg(II), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and Pd(II)]. First, a hydrophilic porphyrin (uroporphyrin I) was found to undergo metalation with all metals examined except Mg(II). Second, a competition experiment among the eight metals with uroporphyrin in limiting quantity afforded preferential metalation with Mn(II), Co(II), Cu(II) and Ni(II). A multicomponent analysis method enabled absorption spectrophotometric detection of 8 distinct uroporphyrins (7 metallo-, 1 free base) in a single mixture. Third, a dione–aminoketone reaction was performed in aqueous solution containing the metals followed by photooxidation in the presence of a quinone. The reaction proceeds through multiple stages: (1) dione–aminoketone condensation to give a pyrrole equipped for self-condensation, (2) tetramerization of the pyrrole and cyclization to give uroporphyrinogens, (3) 6e−/6H+ dehydrogenation (e.g., photooxidation) to give the uroporphyrins, and (4) metalation of the uroporphyrins. The presence versus absence of metals resulted in lower yields, yet Mn(II), Fe(II), Co(II), Cu(II) and Zn(II) each individually gave the corresponding metallouroporphyrin [with trivalent metals observed in three cases: Mn(III), Fe(III), and Co(III)]. Analogous reaction in the presence of all eight metals together gave the free base, Mn(III), and Zn(II) chelates whereas other metal chelates could not be reliably detected by absorption spectroscopy or mass spectrometry. Such metalloporphyrins greatly broaden the accessible redox levels, catalytic avenues, and photochemical features versus those of the free base porphyrins. Taken together, scavenging of metals is expected to increase the functional diversity of tetrapyrroles on early Earth.

  在含有代表性地球有效金属 [Mg(II)、Mn(II)、Fe(II)、Co(II)、Ni(II)、Cu(II) 的水溶液中检查了四吡咯大环形成的生命前模型、Zn(II) 和 Pd(II)]。首先，发现亲水性卟啉（尿卟啉 I）与除 Mg(II) 之外的所有检查金属发生金属化。其次，八种金属与限量的尿卟啉的竞争实验提供了与Mn(II)、Co(II)、Cu(II)和Ni(II)的优先金属化。多组分分析方法能够利用吸收分光光度法检测单一混合物中的 8 种不同的尿卟啉（7 种金属，1 种游离碱）。第三，在含有金属的水溶液中进行二酮-氨基酮反应，然后在醌存在下进行光氧化。该反应经过多个阶段进行：(1) 二酮-氨基酮缩合得到可自缩合的吡咯，(2) 吡咯四聚并环化得到尿卟啉原，(3) 6e−/6H+ 脱氢（例如光氧化）得到尿卟啉，以及(4)尿卟啉的金属化。金属的存在与不存在导致产率较低，但 Mn(II)、Fe(II)、Co(II)、Cu(II) 和 Zn(II) 各自单独产生相应的金属卟啉[在三种情况下观察到三价金属] ：Mn(III)、Fe(III) 和Co(III)]。在所有八种金属一起存在的情况下进行类似反应，得到游离碱、Mn(III) 和 Zn(II) 螯合物，而其他金属螯合物无法通过吸收光谱或质谱法可靠地检测到。与游离碱卟啉相比，此类金属卟啉极大地拓宽了可达到的氧化还原水平、催化途径和光化学特征。总而言之，金属的清除预计将增加早期地球上四吡咯的功能多样性。