(-)-cryptophanol-A

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (-)-cryptophanol-A
• 英文别名: (-)-cryptophanol；14,21,28,35,42-Pentamethoxy-9,12,30,33,43,46-hexaoxadecacyclo[20.20.4.38,37.316,29.113,17.134,38.03,40.019,24.05,49.026,52]tetrapentaconta-1(42),2,5,7,13,15,17(54),19,21,23,26,28,34,36,38(47),40,49,51-octadecaen-7-ol
• 化学式: C₅₃H₅₂O₁₂
• 分子量: 880.989
• InChiKey: WJWCHRQORGWUMJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.2
• 重原子数：
  65
• 可旋转键数：
  5
• 环数：
  20.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  122
• 氢给体数：
  1
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  1,10-二碘癸烷 、 (-)-cryptophanol-A 在 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以25%的产率得到7,14,21,28,35-Pentamethoxy-42-[10-[(14,21,28,35,42-pentamethoxy-9,12,30,33,43,46-hexaoxadecacyclo[20.20.4.38,37.316,29.113,17.134,38.03,40.019,24.05,49.026,52]tetrapentaconta-1(42),2,5,7,13,15,17(54),19,21,23,26,28,34,36,38(47),40,49,51-octadecaen-7-yl)oxy]decoxy]-9,12,30,33,43,46-hexaoxadecacyclo[20.20.4.38,37.316,29.113,17.134,38.03,40.019,24.05,49.026,52]tetrapentaconta-1(42),2,5,7,13,15,17(54),19,21,23,26,28,34,36,38(47),40,49,51-octadecaene
  参考文献：
  名称：

  具有C 1对称性的色氨酸的合成及其手性性质

  摘要：

  新对映体纯cryptophanes 3 - 7具有Ç 1 -symmetry已被合成。电子圆二色性（ECD）和振动圆二色性（VCD）已用于研究其手性，并将其结果与具有D 3对称性的隐甲-A（1）进行了比较。化合物的ECD光谱3 - 7表现出与隐蛋白-A不同的棉花效应。但是，我们的结果表明，可以使用ECD光谱法对单官能化隐色子的绝对构型进行确定的确定。有趣的是，我们发现隐色子的ECD光谱，尤其是1 L b跃迁，对溶剂的性质非常敏感。这些光谱变化基本上是由于整体溶剂的性质，而不是由于特定溶剂插入隐色子腔中的能力所致。另一方面，除了CHCl 3以外，单官能化隐蛋白的VCD光谱相对于CHCl 3 @ cryptophane-A配合物的VCD光谱没有发现显着的光谱修饰。@ 7和较小的CHCl 3 @ 6。通过在DFT（B3PW91 / 6-31G *）级别上进行的从头算起，这些频谱修改基本上包含与隐

  DOI：

  10.1021/jo701662w
• 作为产物：
  描述：

  7,14,21,28,35-pentamethoxy-42-prop-2-enoxy-9,12,30,33,43,46-hexaoxadecacyclo[20.20.4.38,37.316,29.113,17.134,38.03,40.019,24.05,49.026,52]tetrapentaconta-1(42),2,5,7,13,15,17(54),19,21,23,26,28,34,36,38(47),40,49,51-octadecaene 在 palladium diacetate 二乙胺 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 4.0h， 以85%的产率得到(-)-cryptophanol-A
  参考文献：
  名称：

  Cryptophanols, new versatile compounds for the synthesis of functionalized cryptophanes and polycryptophanesElectronic supplementary information (ESI) available: experimental details for compounds 4, 5, 6, 7, 8 and 14. See http://www.rsc.org/suppdata/cc/b1/b109301k/

  摘要：

  在钯催化剂的作用下进行脱保护处理后，单烯丙基化的隐烷-A（1、2）和隐烷-E（3）分别得到了新的隐烷醇 4、5 和 6，它们是制备单官能化隐烷以及设计双隐烷 7 和 8 等大型超分子宿主的重要关键化合物。

  DOI：

  10.1039/b109301k

文献信息

• Novel Synthetic Approach for Optical Resolution of Cryptophanol-A: A Direct Access to Chiral Cryptophanes and Their Chiroptical Properties
  作者：Thierry Brotin、Romain Barbe、Magali Darzac、Jean-Pierre Dutasta

  DOI：10.1002/chem.200204614

  日期：2003.12.5

  material (diastereomeric excess>98 %). Subsequent hydrolysis afforded the optically pure cryptophanol-A enantiomers (+)-2 and (-)-2, which were submitted to nucleophilic substitution reactions to provide cryptophane-A (+)-3 and cryptophane monoester (-)-4 in optically pure form. The chiroptical properties of the new cryptophanes 1-4 were investigated by using circular dichroism spectroscopy, and the absolute

  通过用（-）-樟脑酰氯处理外消旋抗隐烷醇-A（2）以1：1比例获得的一对隐烷非对映异构体1a和1b的结晶分离，提供了大量的光学纯物质（非对映体过量> 98％）。随后水解得到旋光纯的隐花香酚-A对映体（+）-2和（-）-2，将其进行亲核取代反应以提供旋光纯的隐影-A（+）-3和隐影单酯（-）-4。形式。通过使用圆二色性光谱学研究了新的隐烯基1-4的手性性质，并且清楚地确定了分子的绝对构型。这些新的隐体代表了研究相互作用的多发色体系的棉花效应的其他有趣例子。而且，
• Induced Chiroptical Changes of a Water-Soluble Cryptophane by Encapsulation of Guest Molecules and Counterion Effects
  作者：Aude Bouchet、Thierry Brotin、Dominique Cavagnat、Thierry Buffeteau

  DOI：10.1002/chem.200902740

  日期：2010.4.19

  surrounding the cryptophane and whether or not a guest molecule is present inside the cavity of the host. To the best of our knowledge, this is the first example in which the nature of these counterions governs the chiroptical properties of a host molecule. Moreover, specific ECD spectra were obtained depending on the size of the guest molecules. This makes 1 a good sensor for small neutral molecules in aqueous

  我们报告了水溶性隐含酚衍生物1的合成及其两种对映体（> 99％  ee）的旋光性，电子圆二色性（ECD）和振动圆二色性（VCD）的手性性质的研究。我们表明，在基本条件下（pH> 12），隐含酚1在水中表现出不寻常的手性。例如，水中1的ECD和VCD光谱的形状在很大程度上取决于碱金属离子（Li +，Na +，K +，Cs +）围绕着色氨酸以及宿主腔内是否存在客体分子。据我们所知，这是第一个实例，其中这些抗衡离子的性质支配着宿主分子的手性。此外，根据客体分子的大小获得特定的ECD光谱。这使得1个为在水性溶剂中的小的中性分子的好传感器。最后，与DFT计算相关的VCD实验表明，手性变化可以直接与芳香环附近电荷的存在以及封装时烷基链的构象变化直接相关。
• Vibrational Circular Dichroism Study of Optically Pure Cryptophane-A
  作者：Thierry Brotin、Dominique Cavagnat、Jean-Pierre Dutasta、Thierry Buffeteau

  DOI：10.1021/ja0603148

  日期：2006.4.1

  Vibrational circular dichroism (VCD) measurements and density functional theory (DFT) calculations were used to obtain the absolute configuration of optically pure cryptophane-A molecule. This large molecule (120 atoms) that possess a globular shape, but no chiral centers, exceeds the molecular size of published structures for which VCD has been used to determine the absolute configuration. VCD spectra

  振动圆二色性 (VCD) 测量和密度泛函理论 (DFT) 计算用于获得光学纯隐甲-A 分子的绝对构型。这种具有球形形状但没有手性中心的大分子（120 个原子）超过了已使用 VCD 确定绝对构型的已发表结构的分子大小。在 CDCl(3) 溶液中记录的两种解析对映体的 VCD 光谱接近镜像，观察到的 IR 和 VCD 光谱与在 DFT (B3PW91/6-31G) 水平进行的强度计算之间非常吻合，除了绝对配置，氯仿-隐剂-A复合物的脂肪族接头的优先反构象。
• Development of a Functionalized Xenon Biosensor
  作者：Megan M. Spence、E. Janette Ruiz、Seth M. Rubin、Thomas J. Lowery、Nicolas Winssinger、Peter G. Schultz、David E. Wemmer、Alexander Pines

  DOI：10.1021/ja0483037

  日期：2004.11.1

  NMR-based biosensors that utilize laser-polarized xenon offer potential advantages beyond current sensing technologies. These advantages include the capacity to simultaneously detect multiple analytes, the applicability to in vivo spectroscopy and imaging, and the possibility of "remote" amplified detection. Here, we present a detailed NMR characterization of the binding of a biotin-derivatized caged-xenon sensor to avidin. Binding of "functionalized" xenon to avidin leads to a change in the chemical shift of the encapsulated xenon in addition to a broadening of the resonance, both of which serve as NMR markers of ligand-target interaction. A control experiment in which the biotin-binding site of avidin was blocked with native biotin showed no such spectral changes, confirming that only specific binding, rather than nonspecific contact, between avidin and functionalized xenon leads to the effects on the xenon NMR spectrum. The exchange rate of xenon (between solution and cage) and the xenon spin-lattice relaxation rate were not changed significantly upon binding. We describe two methods for enhancing the signal from functionalized xenon by exploiting the laser-polarized xenon magnetization reservoir. We also show that the xenon chemical shifts are distinct for xenon encapsulated in different diastereomeric cage molecules. This demonstrates the potential for tuning the encapsulated xenon chemical shift, which is a key requirement for being able to multiplex the biosensor.