N,N′-(6,6′-(((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene)-bis((pyridin-2-ylmethyl)azanediyl))bis(methylene))bis(pyridine-6,2-diyl))bis(2,2-dimethylpropanamide) | 1404372-24-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: N,N′-(6,6′-(((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene)-bis((pyridin-2-ylmethyl)azanediyl))bis(methylene))bis(pyridine-6,2-diyl))bis(2,2-dimethylpropanamide)
• 英文别名: N-[6-[[[3-[[[6-(2,2-dimethylpropanoylamino)pyridin-2-yl]methyl-(pyridin-2-ylmethyl)amino]methyl]-2-hydroxy-5-methylphenyl]methyl-(pyridin-2-ylmethyl)amino]methyl]pyridin-2-yl]-2,2-dimethylpropanamide
• CAS: 1404372-24-2
• 化学式: C₄₃H₅₂N₈O₃
• 分子量: 728.938
• InChiKey: XECCCJIEOATHMQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  54
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  137
• 氢给体数：
  3
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  [tetraethylammonium][57FeCl4] 、 N,N′-(6,6′-(((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene)-bis((pyridin-2-ylmethyl)azanediyl))bis(methylene))bis(pyridine-6,2-diyl))bis(2,2-dimethylpropanamide) 在 四丁基高氯酸铵 作用下， 以 乙腈 为溶剂， 生成 [⁵⁷Fe^III₂(N,N′-(6,6′-(((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene)-bis((pyridin-2-ylmethyl)azanediyl))bis(methylene))bis(pyridine-6,2-diyl))bis(2,2-dimethylpropanamide)(-H))(OH)]⁴⁺
  参考文献：
  名称：

  Spectroscopic Characterization of the Active Fe^IIIFe^III and Fe^IIIFe^II Forms of a Purple Acid Phosphatase Model System

  摘要：

  Two new dinucleating ligands (H3L2 and HL3), derivatives of a well-known dinucleating ligand (HL1) with two bis-picolylamine sites connected to a bridging phenolate, with hydrogen-bonding donor groups at two of the pyridine moieties were designed and synthesized. Design of these ligands suggests that they will lead to dinuclear complexes with potential to stabilize phosphoester substrates as monodentate rather than bridging ligands. We report the diferric complexes [Fe-2(III)(H2L2)(OH)(4+) and [Fe-2(III)(L-3)(OH)(OH2)(2)](4+), which have been characterized by spectrophotometric titrations, UV-vis, IR, NMR, EPR, and Mossbauer spectroscopy. The phosphatase activity of the diferric systems, in addition to the partially reduced heterovalent [(FeFeII)-Fe-III(L-3)(OH)(OH2)(2)](3+) complex, has been investigated, and the complexes are shown to catalytically hydrolyze the activated phosphodiester substrate BDNPP (bis-dinitrophenylphosphate) as well as the corresponding phosphomonoester substrate DNPP (dinitrophenylphosphate). The results indicate that indeed the secondary interactions lead to an increase of the phosphatase activity and to active phosphomonoesterase catalysts. Interestingly, the heterovalent form of the HL3-based complex is more efficient than the diferric complex, and this is also discussed.

  DOI：

  10.1021/ic301347t
• 作为产物：
  描述：

  2-氨甲基吡啶 在 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 50.5h， 生成 N,N′-(6,6′-(((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene)-bis((pyridin-2-ylmethyl)azanediyl))bis(methylene))bis(pyridine-6,2-diyl))bis(2,2-dimethylpropanamide)
  参考文献：
  名称：

  Spectroscopic Characterization of the Active Fe^IIIFe^III and Fe^IIIFe^II Forms of a Purple Acid Phosphatase Model System

  摘要：

  Two new dinucleating ligands (H3L2 and HL3), derivatives of a well-known dinucleating ligand (HL1) with two bis-picolylamine sites connected to a bridging phenolate, with hydrogen-bonding donor groups at two of the pyridine moieties were designed and synthesized. Design of these ligands suggests that they will lead to dinuclear complexes with potential to stabilize phosphoester substrates as monodentate rather than bridging ligands. We report the diferric complexes [Fe-2(III)(H2L2)(OH)(4+) and [Fe-2(III)(L-3)(OH)(OH2)(2)](4+), which have been characterized by spectrophotometric titrations, UV-vis, IR, NMR, EPR, and Mossbauer spectroscopy. The phosphatase activity of the diferric systems, in addition to the partially reduced heterovalent [(FeFeII)-Fe-III(L-3)(OH)(OH2)(2)](3+) complex, has been investigated, and the complexes are shown to catalytically hydrolyze the activated phosphodiester substrate BDNPP (bis-dinitrophenylphosphate) as well as the corresponding phosphomonoester substrate DNPP (dinitrophenylphosphate). The results indicate that indeed the secondary interactions lead to an increase of the phosphatase activity and to active phosphomonoesterase catalysts. Interestingly, the heterovalent form of the HL3-based complex is more efficient than the diferric complex, and this is also discussed.

  DOI：

  10.1021/ic301347t

文献信息

• An Approach to More Accurate Model Systems for Purple Acid Phosphatases (PAPs)
  作者：Paul V. Bernhardt、Simone Bosch、Peter Comba、Lawrence R. Gahan、Graeme R. Hanson、Valeriu Mereacre、Christopher J. Noble、Annie K. Powell、Gerhard Schenk、Hubert Wadepohl

  DOI：10.1021/acs.inorgchem.5b00628

  日期：2015.8.3

  The active site of mammalian purple acid phosphatases (PAPs) have a dinuclear iron site in two accessible oxidation states (FeIII2 and FeIIIFeII), and the heterovalent is the active form, involved in the regulation of phosphate and phosphorylated metabolite levels in a wide range of organisms. Therefore, two sites with different coordination geometries to stabilize the heterovalent active form and

  哺乳动物紫色酸性磷酸酶（PAP）的活性位点具有双核铁位点，处于两个可访问的氧化态（Fe III 2和Fe III Fe II），杂价是活性形式，参与多种生物体中磷酸盐和磷酸化代谢物水平的调节。因此，据认为催化活性模型系统需要两个具有不同配位几何形状的位点以稳定异价活性形式，另外还具有氢键供体以使得能够固定底物并释放产物。已经详细研究了两个配体及其双核铁配合物。通过X射线晶体学，磁性和Mössbauer光谱学研究的固态结构和性质，以及通过质谱，电子，核磁共振（NMR），电子顺磁共振（EPR）研究的溶液结构和电子性质，和Mössbauer的光谱学和电化学，为了详细了解解的结构和相对稳定性，对它们进行了详细讨论。特别地，对于配体之一，杂价铁通过Fe II 2前体的化学氧化，可以生产III Fe II物种。报道了复合物，特别是杂价复合物的磷酸酶反应性。这些研究包括pH依赖型和底物浓度依赖型研究，从
• Synthesis and characterization of a model complex for flavodiiron NO reductases that stabilizes a diiron mononitrosyl complex
  作者：Hai T. Dong、Yu Zong、Abigail J. Bracken、Michael O. Lengel、Jeff W. Kampf、Debangsu Sil、Carsten Krebs、Nicolai Lehnert

  DOI：10.1016/j.jinorgbio.2022.111723

  日期：2022.4

  in the NO reduction reaction catalyzed by FNORs. In this study, we report the synthesis of a model complex of FNORs with pendant hydrogen bond donors. For this purpose, the ligand H[BPMP] (= 2,6-bis[[bis(2-pyridylmethyl)amino]methyl]-4-methylphenol) was modified with two amide groups in the SCS. Reaction of the precursor complex [Fe2(BPMP(NHCOtBu)2)(OAc)](OTf)2 (1) (OTf− = triflate anion) with NO in

  黄酮二铁 NO 还原酶 (FNOR) 是微生物发病机制中的重要酶，因为它们使微生物对人体免疫防御剂一氧化氮 (NO) 具有抵抗力。DFT 计算预测，第二配位球 (SCS) 氢键网络对于FNOR 催化的 NO 还原反应中的关键 N N 偶联步骤至关重要。在这项研究中，我们报告了具有悬垂氢键供体的 FNOR 模型复合物的合成。为此目的，配体 H[BPMP]（= 2,6-双[[双（2-吡啶基甲基）氨基]甲基]-4-甲基苯酚）在 SCS 中被两个酰胺基团修饰。前体配合物 [Fe 2 (BPMP(NHCO t Bu) 2 )(OAc)](OTf) 2 ( 1 ) (OTf - = 三氟甲磺酸根阴离子）与 NO 在碱存在下导致令人惊讶地分离出二铁单亚硝基配合物 [Fe 2 (BPMP(NHCO t Bu)(NCO t Bu))(OAc)(NO)](OTf) ( 2 ) 和三铁分解产物 [Fe 3 (BPMP(NHCO
• Dinuclear Zinc(II) Complexes with Hydrogen Bond Donors as Structural and Functional Phosphatase Models
  作者：Simone Bosch、Peter Comba、Lawrence R. Gahan、Gerhard Schenk

  DOI：10.1021/ic5009945

  日期：2014.9.2

  It is becoming increasingly apparent that the secondary coordination sphere can have a crucial role in determining the functional properties of biomimetic metal complexes. We have therefore designed and prepared a variety of ligands as metallo-hydrolase mimics, where hydrogen bonding in the second coordination sphere is able to influence the structure of the primary coordination sphere and the substrate binding. The assessment of a structure-function relationship is based on derivates of 2,6-bis[bis(pyridin-2-ylmethyl)amino]methyl}-4-methylphenol (HBPMP = HL1) and 2-[bis(pyridin-2-ylmethyl)amino]methy1}-64[(2-hydroxybenzyl)(pyridin-2-ylmethy)amino]methyl}-4-methylphenol (H2BPBPMP = H2L5), well-known phenolate-based ligands for metallo-hydrolase mimics. The model systems provide similar primary coordination spheres but site-specific modifications in the secondary coordination sphere. Pivaloylamide and amine moieties were chosen to mimic the secondary coordination sphere of the phosphatase models, and the four new ligands H3L2, H3L3, HL4, and H4L6 vary in the type and geometric position of the H-bond donors and acceptors, responsible for the positioning of the substrate and release of the product molecules. Five dinuclear Zn-II complexes were prepared and structurally characterized in the solid, and four also in solution. The investigation phosphatase activity of four model complexes illustrates the impact of the H-bonding network: the Michaelis-Menten constants (catalyst-substrate binding) for all complexes that support hydrogen bonding are smaller than for the reference complex, and this generally leads to higher catalytic efficiency and higher turnover numbers.
• Spectroscopic Characterization of the Active Fe^IIIFe^III and Fe^IIIFe^II Forms of a Purple Acid Phosphatase Model System
  作者：Peter Comba、Lawrence R. Gahan、Valeriu Mereacre、Graeme R. Hanson、Annie K. Powell、Gerhard Schenk、Marta Zajaczkowski-Fischer

  DOI：10.1021/ic301347t

  日期：2012.11.19

  Two new dinucleating ligands (H3L2 and HL3), derivatives of a well-known dinucleating ligand (HL1) with two bis-picolylamine sites connected to a bridging phenolate, with hydrogen-bonding donor groups at two of the pyridine moieties were designed and synthesized. Design of these ligands suggests that they will lead to dinuclear complexes with potential to stabilize phosphoester substrates as monodentate rather than bridging ligands. We report the diferric complexes [Fe-2(III)(H2L2)(OH)(4+) and [Fe-2(III)(L-3)(OH)(OH2)(2)](4+), which have been characterized by spectrophotometric titrations, UV-vis, IR, NMR, EPR, and Mossbauer spectroscopy. The phosphatase activity of the diferric systems, in addition to the partially reduced heterovalent [(FeFeII)-Fe-III(L-3)(OH)(OH2)(2)](3+) complex, has been investigated, and the complexes are shown to catalytically hydrolyze the activated phosphodiester substrate BDNPP (bis-dinitrophenylphosphate) as well as the corresponding phosphomonoester substrate DNPP (dinitrophenylphosphate). The results indicate that indeed the secondary interactions lead to an increase of the phosphatase activity and to active phosphomonoesterase catalysts. Interestingly, the heterovalent form of the HL3-based complex is more efficient than the diferric complex, and this is also discussed.