4-[2-[[12,19-Bis[2-(4-formylphenoxy)ethoxy]-6,13,20-trimethoxy-5-tetracyclo[15.4.0.03,8.010,15]henicosa-1(21),3,5,7,10,12,14,17,19-nonaenyl]oxy]ethoxy]benzaldehyde | 1311229-12-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-[2-[[12,19-Bis[2-(4-formylphenoxy)ethoxy]-6,13,20-trimethoxy-5-tetracyclo[15.4.0.03,8.010,15]henicosa-1(21),3,5,7,10,12,14,17,19-nonaenyl]oxy]ethoxy]benzaldehyde
• CAS: 1311229-12-5
• 化学式: C₅₁H₄₈O₁₂
• 分子量: 852.935
• InChiKey: UCXOIYSJYMSYEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9
• 重原子数：
  63
• 可旋转键数：
  21
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  134
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  三(2-氨基乙基)胺 、 4-[2-[[12,19-Bis[2-(4-formylphenoxy)ethoxy]-6,13,20-trimethoxy-5-tetracyclo[15.4.0.03,8.010,15]henicosa-1(21),3,5,7,10,12,14,17,19-nonaenyl]oxy]ethoxy]benzaldehyde 在 sodium tetrahydroborate 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 22.0h， 生成 2,9,37-Trimethoxy-11,14,32,35,43,46-hexaoxa-20,23,26,52-tetrazanonacyclo[21.19.12.37,36.215,18.228,31.247,50.16,10.04,41.039,58]tetrahexaconta-1,3,6(64),7,9,15(63),16,18(62),28,30,36,38,41,47(56),48,50(55),57,60-octadecaene
  参考文献：
  名称：

  对映纯分子笼的大规模合成：按摩学和识别特性。

  摘要：

  对映纯半胱氨酸-tren（tren =三（2-氨基乙基）胺）衍生物的便捷，高效的克级合成已开发。四步合成基于关键中间体环三藜芦烯的光学分辨率，已对其外消旋化的能垒进行了测量，以确保在合成路径的最后两个步骤中均不发生外消旋化。绝对构型的分配已通过电子圆二色性进行，并且在存在对映纯樟脑磺酸的情况下通过NMR光谱法确定了对映体纯度。为了强调这类化合物的兴趣，研究了去甲肾上腺素神经递质的识别，并显示出对C 3的显着对映选择性对称主机。最后，该高度模块化的合成途径用于提供八个具有不同大小，形状和功能的对映纯半胱氨酸。这些结果强调了这种方法的巨大潜力，这可能导致在手性识别或不对称超分子催化中的许多应用。

  DOI：

  10.1002/chem.201504108
• 作为产物：
  描述：

  对羟基苯甲醛 、 2,7,12-tris-(2-bromoethoxy)-3,8,13-trimethoxy-10,15-dihydro-2H-tribenzo[a,d,g]cyclononene 在 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 生成 4-[2-[[12,19-Bis[2-(4-formylphenoxy)ethoxy]-6,13,20-trimethoxy-5-tetracyclo[15.4.0.03,8.010,15]henicosa-1(21),3,5,7,10,12,14,17,19-nonaenyl]oxy]ethoxy]benzaldehyde
  参考文献：
  名称：

  对映纯分子笼的大规模合成：按摩学和识别特性。

  摘要：

  对映纯半胱氨酸-tren（tren =三（2-氨基乙基）胺）衍生物的便捷，高效的克级合成已开发。四步合成基于关键中间体环三藜芦烯的光学分辨率，已对其外消旋化的能垒进行了测量，以确保在合成路径的最后两个步骤中均不发生外消旋化。绝对构型的分配已通过电子圆二色性进行，并且在存在对映纯樟脑磺酸的情况下通过NMR光谱法确定了对映体纯度。为了强调这类化合物的兴趣，研究了去甲肾上腺素神经递质的识别，并显示出对C 3的显着对映选择性对称主机。最后，该高度模块化的合成途径用于提供八个具有不同大小，形状和功能的对映纯半胱氨酸。这些结果强调了这种方法的巨大潜力，这可能导致在手性识别或不对称超分子催化中的许多应用。

  DOI：

  10.1002/chem.201504108

文献信息

• Large-Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties
  作者：Sara Lefevre、Dawei Zhang、Estelle Godart、Marion Jean、Nicolas Vanthuyne、Jean-Christophe Mulatier、Jean-Pierre Dutasta、Laure Guy、Alexandre Martinez

  DOI：10.1002/chem.201504108

  日期：2016.2.5

  A convenient and efficient gram‐scale synthesis for enantiopure hemicryptophane–tren (tren=tris(2‐aminoethyl)amine) derivatives has been developed. The four‐step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway

  对映纯半胱氨酸-tren（tren =三（2-氨基乙基）胺）衍生物的便捷，高效的克级合成已开发。四步合成基于关键中间体环三藜芦烯的光学分辨率，已对其外消旋化的能垒进行了测量，以确保在合成路径的最后两个步骤中均不发生外消旋化。绝对构型的分配已通过电子圆二色性进行，并且在存在对映纯樟脑磺酸的情况下通过NMR光谱法确定了对映体纯度。为了强调这类化合物的兴趣，研究了去甲肾上腺素神经递质的识别，并显示出对C 3的显着对映选择性对称主机。最后，该高度模块化的合成途径用于提供八个具有不同大小，形状和功能的对映纯半胱氨酸。这些结果强调了这种方法的巨大潜力，这可能导致在手性识别或不对称超分子催化中的许多应用。
• Synthesis and physico-chemical properties of the first water soluble Cu(<scp>ii</scp>)@hemicryptophane complex
  作者：Aline Schmitt、Solène Collin、Christophe Bucher、Vincent Maurel、Jean-Pierre Dutasta、Alexandre Martinez

  DOI：10.1039/c4ob02085e

  日期：——

  A water-soluble metallo-enzyme model featuring a copper(ii) site encaged in a closed-shell cavity of a hemicryptophane has been synthesized and studied.

  一种水溶性金属酶模型已经被合成和研究，它具有铜(ii)位点，被包含在半隐花烷的闭合壳体中。
• Remote Control of Helical Chirality: Thermodynamic Resolution of a Racemic Mixture of CTV Units by Remote Stereogenic Centers
  作者：Bastien Chatelet、Lionel Joucla、Daniele Padula、Lorenzo Di Bari、Guillaume Pilet、Vincent Robert、Véronique Dufaud、Jean-Pierre Dutasta、Alexandre Martinez

  DOI：10.1021/ol5035194

  日期：2015.2.6

  Enantiopure hemicryptophanes designed from the cyclotriveratrylene (CTV) unit display remarkable properties in selective host-guest recognition or as supramolecular catalysts. The unprecedented control of the helical chirality of the CTV unit by remote stereogenic centers of a tren moiety is reported, providing an original access to this highly promising class of host molecules. Although the chiral centers and the CTV unit are separated by more than 10 angstrom, one single diastereomer is formed; the nature of the diastereoselective process is discussed and the procedure is exemplified using different enantiopure tren derivatives. This work also highlights the influence of the chirality of the CTV unit on the whole cage structure.
• Shorter and Modular Synthesis of Hemicryptophane-tren Derivatives
  作者：Bastien Chatelet、Elina Payet、Olivier Perraud、Pascal Dimitrov-Raytchev、Laure-Lise Chapellet、Véronique Dufaud、Alexandre Martinez、Jean-Pierre Dutasta

  DOI：10.1021/ol201355t

  日期：2011.7.15

  Hemicryptophanes are host molecules with many applications as supramolecular catalysts or in ion selective recognition. A very convenient and efficient modular approach for the synthesis of hemicryptophane-tren (tren, tris(2-aminoethyl)-amine) derivatives has been developed. For instance, hemicryptophane 1 was synthesized at the gram scale in four steps from vanillyl alcohol compared to the previous seven-step procedure. The size, shape, and functionalities of the molecular cavity were also easily modified.
• Synthesis of the First Water-Soluble Hemicryptophane Host: Selective Recognition of Choline in Aqueous Medium
  作者：Aline Schmitt、Vincent Robert、Jean-Pierre Dutasta、Alexandre Martinez

  DOI：10.1021/ol500706z

  日期：2014.5.2

  The first water-soluble hemicryptophane cage compound, 4, was synthesized in seven steps from commercially available products, and its complexation properties were studied. NMR and ITC experiments indicate that 4 is an efficient receptor for choline in water (Delta G degrees = -5.2 kcal mol(-1)). High substrate selectivity was achieved since no complexation was observed for its closely related substrates: glycine betaine and betaine aldehyde. Density functional theory calculations were performed to analyze the interactions that are involved in the formation of the inclusion complex.