N,N'-(6,6'-azanediylbis(methylene)bis(pyridine-6,2-diyl))bis(2,2-dimethylpropanamide) | 831195-46-1

• 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'-azanediylbis(methylene)bis(pyridine-6,2-diyl))bis(2,2-dimethylpropanamide)
• 英文别名: N,N-bis((2-pivaloylamidopyridin-6-yl)methyl)amine；bis[N-(6-pivalamidopyridin-2-ylmethyl)]amine；bis-(6-pivaloylamido-2-pyridylmethyl)amine；bis(6-pivalamido-2-pyridylmethyl)-amine；bis(6-pivalamide-2-pyridylmethyl)amine
• CAS: 831195-46-1
• 化学式: C₂₂H₃₁N₅O₂
• 分子量: 397.52
• InChiKey: ZDQROWHPNILKLZ-UHFFFAOYSA-N

物化性质

• 沸点：
  625.5±55.0 °C(Predicted)
• 密度：
  1.157±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.74
• 重原子数：
  29.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  96.01
• 氢给体数：
  3.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  N,N'-(6,6'-azanediylbis(methylene)bis(pyridine-6,2-diyl))bis(2,2-dimethylpropanamide) 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 18.5h， 生成 (bis((6-(neopentylamino)pyridinyl)methyl)amino)-2-methylpropane-2-thiol
  参考文献：
  名称：

  非血红素铁 (III) 超氧化物复合物导致硫氧化

  摘要：

  报道了一种新的烷基硫醇盐连接的非血红素铁络合物 Fe II (BNPA Me2 S)Br ( 1 )。 1与 O 2在 -40 °C 下反应，或三价铁形式与 O 2 •–在 -80 °C 下反应，得到稀有的铁(III)-超氧化物中间体，[Fe III (O 2 )(BNPA Me2) S)] + ( 2 )，通过 UV-vis、 57 Fe 穆斯堡尔、ATR-FTIR、EPR 和 CSIMS 进行表征。然后亚稳态2通过涉及亚磺酸铁中间体的连续 O 原子转移机制转化为 S-氧化 Fe II （亚磺酸盐）产物。这些结果为硫醇双加氧酶中所提出的中间体的可行性提供了证据。

  DOI：

  10.1021/jacs.3c12337
• 作为产物：
  描述：

  N,N'-(6,6'-(2-nitrophenylsulfonylazanediyl)bis(methylene)bis(pyridine-6,2-diyl))bis(2,2-dimethylpropanamide) 在 potassium carbonate 、 苯硫酚 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 以92%的产率得到N,N'-(6,6'-azanediylbis(methylene)bis(pyridine-6,2-diyl))bis(2,2-dimethylpropanamide)
  参考文献：
  名称：

  Novel asymmetrically functionalized bis-dipicolylamine metal complexes: peripheral decoration of a potent anion recognition scaffold

  摘要：

  我们报告了一类新型非对称官能化的、双位点双吡啶甲胺(BDPA)配体的设计和合成。这项研究的一个关键特征是对一个高效分子识别骨架进行可控的、序列性的官能团修饰。量热筛选鉴定出一种BDPA类似物作为无机磷酸盐的高效(Ka∼106 M−1)和选择性传感器。

  DOI：

  10.1039/b917692f

文献信息

• Role of the Secondary Coordination Sphere in Metal-Mediated Dioxygen Activation
  作者：Ryan L. Shook、A. S. Borovik

  DOI：10.1021/ic901550k

  日期：2010.4.19

  are clear connections between control of the secondary coordination sphere and the ability of metal complexes to (1) reversibly bind dioxygen or (2) bind and activate dioxygen to form highly reactive metal−oxo complexes. In this Forum Article, several biological and synthetic examples are presented and discussed in terms of structure−function relationships. Particular emphasis is given to systems with

  Alfred Werner 在近 100 年前提出，二次配位层在决定过渡金属配合物的物理性质方面发挥着重要作用。我们现在知道，二级配位层几乎影响过渡金属化学的所有方面，包括金属介导过程中的反应性和选择性。这些特征在过渡金属配合物对分子氧的结合和活化中得到了突出体现。二级配位层的控制与金属配合物（1）可逆地结合分子氧或（2）结合并活化分子氧形成高反应性金属-氧配合物的能力之间存在明显的联系。在这篇论坛文章中，从结构与功能关系的角度提出并讨论了几个生物和合成的例子。特别强调具有确定的非共价相互作用的系统，例如涉及双氧衍生配体的分子内氢键。为了进一步说明这些效应，描述了具有碱性氧配体的金属-氧配合物对CH键的均裂。
• Self-assembled monolayer electrode of a diiron complex with a phenoxo-based dinucleating ligand: observation of molecular oxygenadsorption/desorption in aqueous media
  作者：Tomohiko Inomata、Kazuma Shinozaki、Yuya Hayashi、Hidekazu Arii、Yasuhiro Funahashi、Tomohiro Ozawa、Hideki Masuda

  DOI：10.1039/b711802c

  日期：——

  dinucleating ligand, 2,6-bis[bis(6-pivalamido-2-pyridylmethyl)amino-methyl-4-aminophenol (1), and its Fe2(II) complex, [Fe2(II)(1)(PhCOO)2](CF3SO3) (2), were prepared and 2 deposited on the Au surface (2/Au) is much more stable than in solution and exhibits redox behavior in aqueous media as well as reversible adsorption/desorption of oxygen at room temperature.

  基于苯氧的双核配体2,6-双[双（6-新戊基-2-吡啶基甲基）氨基-甲基-4-氨基苯酚（1）及其Fe2（II）络合物[Fe2（II）（1）制备了（PhCOO）2]（CF3SO3）（2），沉积在Au表面（2 / Au）上的2比溶液中的稳定得多，并且在水性介质中表现出氧化还原行为，并且在20°C时可逆地吸附/解吸氧室内温度。
• Investigating the effect of hydrogen bonding environments in amide cleavage reactions at zinc(ii) complexes with intramolecular amide oxygen co-ordination
  作者：Juan C. Mareque Rivas、Emiliano Salvagni、Simon Parsons

  DOI：10.1039/b414223c

  日期：——

  ligands without hydrogen bonding groups (1,10-phenanthroline L5, 2-(aminomethyl)pyridine L6) as control compounds, and with an amino hydrogen bonding group (6-amino-2-(aminomethyl)pyridine L7) have been synthesised. Amide cleavage is in this case faster at the zinc(II) complex with the amino hydrogen bonding group. Thus, hydrogen bonding environments can both accelerate and slow down amide bond cleavage reactions

  酰胺键与氢键合微环境周围的锌（II）离子配位是金属蛋白酶的常见结构/功能特征。我们报告了两种策略将氢键基团定位在锌（II）结合的酰胺氧附近，并且我们研究了它们对酰胺基团稳定性的影响。多齿三脚架配体（6-R1-2-吡啶甲基）-R2（R1 = NHCOtBu，R2 = N（CH2-py-6-X）2 X = H L1，X = NH2，H L2，X = NH2 L3）形式[（L）Zn] 2+阳离子（L = L1，1; L2，2; L3，3）带有分子内酰胺氧配位（1-3）和分子内NH ... O = C（酰胺）氢由配体骨架牢固固定的键（2，3）。当在50（1）摄氏度下在甲醇中添加Me4NOH.5H2O（1当量）时，1-3进行叔丁基酰胺的裂解。在这些条件下，酰胺的半衰期t（1/2）粘结时间为0.4 h，持续1 2小时9小时，3小时320小时。（6-NHCOtBu-2-吡啶基甲基）-R2（R2 = N（
• 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.
• Structural Diversity in Metal Complexes with a Dinucleating Ligand Containing Carboxyamidopyridyl Groups
  作者：Gary K.-Y. Ng、Joseph W. Ziller、A. S. Borovik

  DOI：10.1021/ic200881t

  日期：2011.9.5

  The synthesis of a (carboxyamido)pyridinepyrazolate (H(5)bppap) dinucleating lipid is described. Bimetallic iron and cobalt complexes of Hsbppap ([M(2)(II)H(2)bppap](+)) showed structural differences in both their primary and secondary coordination spheres. The binding of small molecules into the preorganized ligand cavity is verified by the hydration of [Fe(2)(II)H(2)bppap](+) and [Co(2)(II)H(2)bppap](+), leading to the formation of complexes [Co-II(OH)}-Co(II)H(3)bppap](+) and [Fe-II(OH)}Fe(II)H(3)bppap](+), in which one of the metal centers has a terminal hydroxo ligand.