1-methyl-4-oxo-2,6-bis(2-pyridyl)piperidine-3,5-dicarboxylic acid dimethyl ester | 94543-37-0

• 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: 1-methyl-4-oxo-2,6-bis(2-pyridyl)piperidine-3,5-dicarboxylic acid dimethyl ester
• 英文别名: dimethyl 1-methyl-4-oxo-2,6-bis(pyridin-2-yl)piperidine-3,5-dicarboxylate；dimethyl 1-methyl-4-oxo-2,6-di(pyridin-2-yl)piperidine-3,5-dicarboxylate；dimethyl N-methyl-4-oxo-2,6-di(2-pyridyl)-4-piperidine-3,5-dicarboxylate；bis(pyridyl)piperidone；1'-methyl-4'-oxo-1',2',3',4',5',6'-hexahydro-[2,2';6',2'']terpyridine-3',5'-dicarboxylic acid dimethyl ester；dimethyl 2,6-di-(2-pyridyl)-1-methyl-piperid-4-one-3,5-dicarboxylate；1-Methyl-2,6-dipyridyl-3,5-di(methoxy-carbonyl)-4-piperidone；dimethyl 1-methyl-4-oxo-2,6-dipyridin-2-ylpiperidine-3,5-dicarboxylate
• CAS: 94543-37-0
• 化学式: C₂₀H₂₁N₃O₅
• 分子量: 383.404
• InChiKey: GUIZEUZIGCGSIF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  98.7
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1-methyl-4-oxo-2,6-bis(2-pyridyl)piperidine-3,5-dicarboxylic acid dimethyl ester 在 sodium tetrahydroborate 作用下， 以 1,4-二氧六环 、 乙醇 、 水 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  CuII-selective bispidine–dye conjugates

  摘要：

  The substitution of tetradentate bispidine ligands with rhodamine and cyanine dye molecules, coupled to an amine donor, forming an amide as potential fifth donor, is described. Bispidines are known to lead to very stable Cu-II complexes, and the coordination to Cu-II was expected to efficiently quench the fluorescence of dye molecules. However, at physiological pH the amide is not coordinated, as shown by titration experiments and crystallographic structural data of three possible isomers of these complexes. This may be due to the specific cavity shape of bispidines and the Jahn-Teller lability of the Cu-II center. While Cu-II coordination in aqueous solution leads to efficient fluorescence quenching, experiments show that the complex stabilities are not large enough for Cu-II sensing in biological media, and possibilities are discussed, how this may be achieved by optimized bispidine-dye conjugates. (C) 2015 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.jinorgbio.2015.05.009
• 作为产物：
  描述：

  1,3-丙酮二羧酸二甲酯 、 甲胺 以 异丁醇 、 水 为溶剂， 反应 1.67h， 以88%的产率得到1-methyl-4-oxo-2,6-bis(2-pyridyl)piperidine-3,5-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  WO2006/133869

  摘要：

  公开号：

文献信息

• Fluorous bispidine: a bifunctional reagent for copper-catalyzed oxidation and knoevenagel condensation reactions in water
  作者：Wei Jie Ang、Yong Sheng Chng、Yulin Lam

  DOI：10.1039/c5ra17093a

  日期：——

  Fluorous bispidine-type ligands have been developed to demonstrate its bifunctional property as a ligand and base in copper-catalyzed aerobic oxidation, the Knoevenagel condensation and tandem oxidation/condensation in water under mild conditions.

  氟亲和性双咪唑型配体已被开发用于展示其在铜催化的氧化反应、Knoevenagel缩合和水中温和条件下串联氧化/缩合反应中作为配体和碱的双功能性质。
• BISPIDON LIGANDS AND THE METAL COMPLEXES THEREOF
  申请人：Comba Peter

  公开号：US20110003984A1

  公开（公告）日：2011-01-06

  The present invention relates to novel bispidon ligands, a method for the production thereof, and the use thereof as a ligand in metal complexes and the selective separation of metals, metal complexes comprising said ligands, method for the production thereof, and the use of such metal complexes in organic synthesis, in bleaching, and in the radiopharmaceutical field.

  本发明涉及新的双螯配体，其生产方法以及将其用作金属配合物中的配体和金属的选择性分离，包括该配体的金属配合物，其生产方法以及在有机合成、漂白和放射性药物领域中使用这种金属配合物的方法。
• Optimization of the Efficiency of Oxidation Catalysts Based on Iron Bispidine Complexes
  作者：Peter Comba、Hubert Wadepohl、Sebastian Wiesner

  DOI：10.1002/ejic.201100212

  日期：2011.6

  High-valent bispidine iron-oxo complexes are among the most efficient nonheme iron oxidation catalysts. Here, we report the synthesis and structural analysis of two derivatives of the known pentadentate bispidine ligand L1 L1 = 2,4-pyridyl-7-(pyridine-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonane}: L2 and L3 L2 = 2,4-pyridyl-7-[1-(pyridine-2-yl)ethyl]-3,7-diazabicyclo[3.3.1]nonane; L3 = 2,4-pyridyl-

  高价双吡啶铁氧配合物是最有效的非血红素铁氧化催化剂之一。在这里，我们报告了已知五齿双吡啶配体 L1 L1 = 2,4-pyridyl-7-(pyridine-2-ylmethyl)-3,7-diazabicyclo[3.3.1]nonane} 的两种衍生物的合成和结构分析: L2 和 L3 L2 = 2,4-吡啶基-7-[1-(吡啶-2-基)乙基]-3,7-二氮杂双环[3.3.1]壬烷；L3 = 2,4-吡啶基-7-[苯基(吡啶-2-基)甲基]-3,7-二氮杂双环[3.3.1]壬烷}及其FeII配合物。环辛烯和苯乙烯以碘代苯为氧化剂的催化环氧化的产率从L1-到L2-再到L3-基催化剂（例如，在厌氧条件下，以MeCN为溶剂的氧化苯乙烯的产率为40% , 90 %, 96 %)，这与 FeIII/II 还原电位 [Fe(L1)(NCMe)]n+ (1.01 V) 相关，[Fe(L2)(NCMe)]n+
• The Mechanism of the (Bispidine)copper(II)-Catalyzed Aziridination of Styrene: A Combined Experimental and Theoretical Study
  作者：Peter Comba、Carolin Lang、Carlos Lopez de Laorden、Amsaveni Muruganantham、Gopalan Rajaraman、Hubert Wadepohl、Marta Zajaczkowski

  DOI：10.1002/chem.200701910

  日期：2008.6.9

  aziridination mechanism and the catalytic activity of (bispidine)copper(I) and -copper(II) complexes are reported and discussed (bispidine=tetra- or pentadentate 3,7-diazabicyclo[3.1.1]nonane derivative with two or three aromatic N donors in addition to the two tertiary amines). There is a correlation between the redox potential of the copper(II/I) couple and the activity of the catalyst. The most active catalyst

  报道并讨论了关于（双吡啶）铜（I）和-铜（II）配合物的叠氮化机理和催化活性的实验和基于DFT的计算结果（双吡啶=四齿或五齿3,7-二氮杂双环[3.1.1]壬烷衍生物，除了两个叔胺外，还带有两个或三个芳族氮供体。铜（II / I）对的氧化还原电势与催化剂的活性之间存在相关性。研究的最具活性的催化剂在所有（双吡啶）铜（II）配合物中具有最高的氧化还原电势，可在30分钟内完成180次转换。详细的混合密度泛函理论（DFT）研究可深入了解反应性中间体和过渡态的结构，自旋态和稳定性，铜中心的氧化态以及腈源的密度。在形成氮丙啶产物的可能途径中，两个NC键的逐步形成被证明是优选的，这也来自实验结果。尽管催化活性铜氮烯的三重态在能量上最低，但​​是自由基中间体的两种可能的自旋态实际上是简并的，并且在此阶段存在自旋交叉，因为对单重态产物的三重态能垒非常高。
• Bifunctional bispidine derivatives for copper-64 labelling and positron emission tomography
  作者：Amandine Roux、Raphaël Gillet、Sandrine Huclier-Markai、Laurence Ehret-Sabatier、Loïc J. Charbonnière、Aline M. Nonat

  DOI：10.1039/c6ob02712a

  日期：——

  analogue of L1 (L2) has been obtained by introducing an L-lysine amino acid on the bispidine skeleton. Ligand L2 demonstrates good radiolabelling capacities at room temperature and in water (pH 4 to pH 6). This new bispidine is a versatile platform which can easily react with NHS esters and can be subsequently coupled to a recognition unit in order to perform targeted Positron Emission Tomography (PET)

  首次报道了用64 Cu取代甘氨酸酯侧链（L 1）的联吡啶（3,7-二氮杂双环[3.3.1]壬烷）衍生物的首次放射性标记研究。在室温下和宽范围的pH值下均可快速简便地进行标记。在这些条件下，在微摩尔浓度的配体下，在5分钟内达到了90％以上的放射化学收率。L 1（L 2）的双功能类似物已通过在联吡啶骨架上引入L-赖氨酸氨基酸而获得。配体L 2在室温和水中（pH 4至pH 6）具有良好的放射性标记能力。这种新型的双联吡啶是一种多功能平台，可以轻松地与NHS酯反应，并且可以随后与识别单元偶联，以进行靶向正电子发射断层扫描（PET）成像。作为概念证明，已经合成了具有生物素（L 3）或马来酰亚胺官能团（L 4）的两个新的双功能螯合剂（BFC）。生物素化的BFC对于使用链霉亲和素偶联抗体的预靶向策略非常有价值。马来酰亚胺衍生物L 4的反应性已经使用模型肽GP120进行了研究。在生理条件下已经实现了定量偶