(2R,2'R,3R,3'R)-2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(methylene)bis(3-(benzyloxy)tetrahydro-2H-pyran) | 1198807-22-5

• 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: (2R,2'R,3R,3'R)-2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(methylene)bis(3-(benzyloxy)tetrahydro-2H-pyran)
• 英文别名: (2R,3R)-3-phenylmethoxy-2-[2-[2-[[(2R,3R)-3-phenylmethoxyoxan-2-yl]methoxy]ethoxy]ethoxymethyl]oxane
• CAS: 1198807-22-5
• 化学式: C₃₀H₄₂O₇
• 分子量: 514.659
• InChiKey: QHKBIDBKFWZCGT-SKKKGAJSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  37
• 可旋转键数：
  16
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  64.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (2R,2'R,3R,3'R)-2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(methylene)bis(3-(benzyloxy)tetrahydro-2H-pyran) 在 氢气 、 palladium(II) hydroxide 、 sodium hydride 作用下， 以 四氢呋喃 、 乙酸乙酯 、 mineral oil 为溶剂， 反应 7.0h， 生成 (1R,9R,14R,24R)-2,5,8,13,16,19,22,25-octaoxatricyclo[22.4.0.09,14]octacosane
  参考文献：
  名称：

  Correlation between Conformational Equilibria of Free Host and Guest Binding Affinity in Non-preorganized Receptors

  摘要：

  Positive cooperativity between host conformational equilibria and guest binding has been widely reported in protein receptors. However, reported examples of this kind of cooperativity in synthetic hosts are scarce and largely serendipitous, among other things because it is hard to envision systems which display this kind of cooperativity. In order to shed some light on the correlation between conformational equilibria of free host and guest binding, selected structural modifications have been performed over a family of nonpreorganized hosts in order to induce conformational changes and to analyze their effect on the binding affinity. The conformational effect was evaluated by a theoretical conformational search and correlated with the ability of the receptors. All data suggest that those receptors that display the best association constants are able to sample folded conformations analogous to the conformational requirements for the binding of the guests. On the contrary, for those receptors where folded conformers are scarce, then the association constant and enantioselectivity clearly drop.

  DOI：

  10.1021/jo400683j
• 作为产物：
  描述：

  (4aR,8aR)-2-Phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine 在 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 mineral oil 为溶剂， 反应 7.5h， 生成 (2R,2'R,3R,3'R)-2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(methylene)bis(3-(benzyloxy)tetrahydro-2H-pyran)
  参考文献：
  名称：

  Correlation between Conformational Equilibria of Free Host and Guest Binding Affinity in Non-preorganized Receptors

  摘要：

  Positive cooperativity between host conformational equilibria and guest binding has been widely reported in protein receptors. However, reported examples of this kind of cooperativity in synthetic hosts are scarce and largely serendipitous, among other things because it is hard to envision systems which display this kind of cooperativity. In order to shed some light on the correlation between conformational equilibria of free host and guest binding, selected structural modifications have been performed over a family of nonpreorganized hosts in order to induce conformational changes and to analyze their effect on the binding affinity. The conformational effect was evaluated by a theoretical conformational search and correlated with the ability of the receptors. All data suggest that those receptors that display the best association constants are able to sample folded conformations analogous to the conformational requirements for the binding of the guests. On the contrary, for those receptors where folded conformers are scarce, then the association constant and enantioselectivity clearly drop.

  DOI：

  10.1021/jo400683j

文献信息

• Quantification of a CH-π Interaction Responsible for Chiral Discrimination and Evaluation of Its Contribution to Enantioselectivity
  作者：Romen Carrillo、Matías López-Rodríguez、Victor S. Martín、Tomás Martín

  DOI：10.1002/anie.200903281

  日期：2009.10.5

  things come in small interactions: The high chiral discrimination displayed by a new receptor with ammonium salts of aromatic α‐amino acid methyl esters is mainly the result of one of the weakest noncovalent interactions, the CH–π interaction (see picture). The interaction has been identified and quantified, and its contribution to the chiral recognition process has been evaluated.

  好的事情是发生小的相互作用：新的受体与芳香族α-氨基酸甲酯的铵盐表现出的高度手性区别主要是最弱的非共价相互作用之一，即CH-π相互作用的结果（见图）。相互作用已被识别和量化，并已评估其对手性识别过程的贡献。
• A Novel Approach for the Evaluation of Positive Cooperative Guest Binding: Kinetic Consequences of Structural Tightening
  作者：Romen Carrillo、Ezequiel Q. Morales、Víctor S. Martín、Tomás Martín

  DOI：10.1002/chem.201300583

  日期：2013.5.27

  within receptors upon binding. According to such an interpretation, positive cooperative binding operates through structural tightening. Hence, a quite counterintuitive kinetic behavior for positively cooperative bound complexes may be postulated: the more stable the complex, the slower it is formed. Such a hypothesis was tested in a synthetic system in which positive cooperative binding was previously confirmed

  合作性是生物分子显示的最相关的功能之一。因此，超分子化学领域的挑战之一是了解协同结合效应的潜在机制。传统上，合作性与多价受体有关，但是Williams等人。已经基于结合后受体内非共价相互作用的增强提出了不同的解释。根据这种解释，积极的合作约束是通过结构性紧缩来进行的。因此，可以假定对于正合作结合的复合物来说，其动力学行为是违反直觉的：复合物越稳定，形成的速度就越慢。这种假设在合成系统中进行了测试，在该系统中，先前已通过量热实验确认了积极的合作结合。的确，G °）和客体结合动力学（ΔG ≠）证实了预期的行为。这些独特的动力学提供了积极的客体结合的确凿证据，考虑到动力学实验在合成和生物系统中都经常且准确地进行，这一点特别有用。
• Correlation between Conformational Equilibria of Free Host and Guest Binding Affinity in Non-preorganized Receptors
  作者：Romen Carrillo、Ezequiel Q. Morales、Víctor S. Martín、Tomás Martín

  DOI：10.1021/jo400683j

  日期：2013.8.16

  Positive cooperativity between host conformational equilibria and guest binding has been widely reported in protein receptors. However, reported examples of this kind of cooperativity in synthetic hosts are scarce and largely serendipitous, among other things because it is hard to envision systems which display this kind of cooperativity. In order to shed some light on the correlation between conformational equilibria of free host and guest binding, selected structural modifications have been performed over a family of nonpreorganized hosts in order to induce conformational changes and to analyze their effect on the binding affinity. The conformational effect was evaluated by a theoretical conformational search and correlated with the ability of the receptors. All data suggest that those receptors that display the best association constants are able to sample folded conformations analogous to the conformational requirements for the binding of the guests. On the contrary, for those receptors where folded conformers are scarce, then the association constant and enantioselectivity clearly drop.