(11Z,13Z)-14-fluororetinal | 68200-22-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (11Z,13Z)-14-fluororetinal
• 英文别名: (2Z,4Z,6E,8E)-2-fluoro-3,7-dimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,4,6,8-tetraenal
• CAS: 68200-22-6
• 化学式: C₂₀H₂₇FO
• 分子量: 302.432
• InChiKey: KCEVSZISNGMYIB-IESXUTTNSA-N

物化性质

• 沸点：
  431.2±20.0 °C(predicted)
• 密度：
  0.991±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (11Z,13Z)-14-fluororetinal 以 正己烷 、 氯仿 为溶剂， 生成
  参考文献：
  名称：

  A ¹⁹F NMR Study of Rhodopsin Analogs:  Use of Vinylfluororetinal Chromophores

  摘要：

  F-19 NMR spectra of 11-cis and 9-cis isomers of six fluorinated rhodopsin analogs with the label(s) located at the vinylic positions of the polyene chain (8-F, 10-F, 12-F, 14-F, 8,12-F-2, 10,14-F-2) are reported along with their UV-vis and CD spectra. The regiospecific F chemical shift data are analyzed in terms of chromophore changes and local perturbation resulting from specific interactions with protein. Two analogs (11-cis-12-F and 11-cis-8-F) and also 9,11-di-cis-12-F possess FOS (fluorine opsin shift) values uniquely different from others. Ab initio F NMR chemical shielding calculations of model structures provide support that a strong protein perturbation to the 12-F position prevails in the binding cavity and that F-8 shift is sensitive to variation of the nearby dihedral angle(s). Possible causes for the broad line width of the F signals of these membrane proteins are discussed.

  DOI：

  10.1021/jp952850k
• 作为产物：
  描述：

  (7E,9E)-beta-离子亚基乙醛 在 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 、 Petroleum ether 为溶剂， 反应 1.0h， 生成 (11Z,13Z)-14-fluororetinal
  参考文献：
  名称：

  通过 C15 + C5 路线制备 (all-E)- 和 (11Z)-12-Haloretinals 和 (11Z,13Z)- 和 (13Z)-14-Haloretinals ? 探索在共轭尾的任何位置制备任何经过合理化学修饰的类视黄醇的可能性

  摘要：

  在本文中，我们描述了如何通过亲电取代以简单的方式制备化学修饰的叶立德。随后的 Horner-Emmons 反应可以得到 (all-E)- 和 (11Z)-12-chloro-、-12-bromo- 和 -12-iodoretal。可以预期，以这种方式可以制备更多在 12 位进行化学修饰的视黄醛。Selectfluor® 是一种通过亲电取代引入氟原子的良好试剂，不会产生 12-氟视黄醛系统。然而，14-氟视黄醛可通过阴离子与 Selectfluor® 的反应轻松获得。Cl、Br 和 I 原子也以 (11Z,13Z)- 和 (13Z)-异构形式引入视黄醛的 14 位。这种策略可以扩展到整个范围的亲电取代反应。我们还开发了一种制备 4-羟基取代的 Horner-Emmons 衍生物的新方法，该方法可以通过与（二乙氨基）三氟化硫 (DAST) 反应转化为 4-氟衍生物。该系统可以简单地转化为 (all-E)-

  DOI：

  10.1002/ejoc.200400488

文献信息

• Fluoro Derivatives of Retinal Illuminate the Decisive Role of the C₁₂-H Element in Photoisomerization and Rhodopsin Activation
  作者：Petra H. M. Bovee-Geurts、Isabelle Fernández Fernández、Robert S. H. Liu、Richard A. Mathies、Johan Lugtenburg、Willem J. DeGrip

  DOI：10.1021/ja907577p

  日期：2009.12.16

  Rhodopsin, the visual pigment of the vertebrate rod cell, is among the best investigated members of the G-protein-coupled receptor family. Within this family a unique characteristic of visual pigments is their covalently bound chromophore, 11-cis retinal, which acts as an inverse agonist. Upon illumination it can be transformed into the all-trans isomer that acts as a full agonist. This photoisomerization process is extremely efficient: 2 out of 3 photons are effective, full stereoselectivity is achieved, and stereoinversion occurs within 200 fs. The mechanism behind this process is still not really understood, although the available evidence points at the twisted C-9-C-13 segment of the 11-cis ligand as the quintessence. To further dissect the role of this segment, we have generated the 10-fluoro, 12-fluoro, and 14-fluoro analogues of rhodopsin. A fluoro substituent brings in only little more volume than hydrogen, but considerably more mass and polarizability. The analogue pigments were compared to rhodopsin with respect to their photosensitivity (quantum yield), light-induced structural transitions (UV-vis and FT-IR spectroscopy), and signaling activity (G protein activation rate). We find that 14-F substitution is quite neutral, while 10-F and 12-F substitutions exert significant but distinct effects. The 10-F pigment exhibits a quantum yield similar to that of rhodopsin (0.65) but strongly perturbed thermodynamics of the structural transitions following photoactivation and only 20% of the native signaling activity. The 12-F pigment exhibits a significantly decreased quantum yield (0.47) and signaling activity (30%) but mixed effects on the structural transitions. These properties are compared to those of the corresponding methyl derivatives. We conclude that rotation of the C-12-H bond of the rhodopsin chromophore is a major rate-limiting factor in the photoisomerization process, while the C-10-H moiety plays a dominant role in ligand relaxation and further rearrangements following photoactivation.
• Preparation of (all-E)- and (11Z)-12-Haloretinals and (11Z,13Z)- and (13Z)-14-Haloretinals by the C15 + C5 Route ? Exploring the Possibility of Preparing any Retinoid Rationally Chemically Modified at any Position in the Conjugated Tail
  作者：Yajie Wang、Johan Lugtenburg

  DOI：10.1002/ejoc.200400488

  日期：2004.12

  that many more retinals chemically modified at the 12-position could be prepared in this manner. Selectfluor®, a good reagent for introducing a fluorine atom by electrophilic substitution, does not give the 12-fluororetinal system. However, 14-fluororetinal is simply available by reaction of the anion with Selectfluor®. Cl, Br and I atoms were also introduced at the 14-position of retinal both in the

  在本文中，我们描述了如何通过亲电取代以简单的方式制备化学修饰的叶立德。随后的 Horner-Emmons 反应可以得到 (all-E)- 和 (11Z)-12-chloro-、-12-bromo- 和 -12-iodoretal。可以预期，以这种方式可以制备更多在 12 位进行化学修饰的视黄醛。Selectfluor® 是一种通过亲电取代引入氟原子的良好试剂，不会产生 12-氟视黄醛系统。然而，14-氟视黄醛可通过阴离子与 Selectfluor® 的反应轻松获得。Cl、Br 和 I 原子也以 (11Z,13Z)- 和 (13Z)-异构形式引入视黄醛的 14 位。这种策略可以扩展到整个范围的亲电取代反应。我们还开发了一种制备 4-羟基取代的 Horner-Emmons 衍生物的新方法，该方法可以通过与（二乙氨基）三氟化硫 (DAST) 反应转化为 4-氟衍生物。该系统可以简单地转化为 (all-E)-
• A ¹⁹F NMR Study of Rhodopsin Analogs:  Use of Vinylfluororetinal Chromophores
  作者：Leticia U. Colmenares、Walter P. Niemczura、Alfred E. Asato、Robert S. H. Liu

  DOI：10.1021/jp952850k

  日期：1996.1.1

  F-19 NMR spectra of 11-cis and 9-cis isomers of six fluorinated rhodopsin analogs with the label(s) located at the vinylic positions of the polyene chain (8-F, 10-F, 12-F, 14-F, 8,12-F-2, 10,14-F-2) are reported along with their UV-vis and CD spectra. The regiospecific F chemical shift data are analyzed in terms of chromophore changes and local perturbation resulting from specific interactions with protein. Two analogs (11-cis-12-F and 11-cis-8-F) and also 9,11-di-cis-12-F possess FOS (fluorine opsin shift) values uniquely different from others. Ab initio F NMR chemical shielding calculations of model structures provide support that a strong protein perturbation to the 12-F position prevails in the binding cavity and that F-8 shift is sensitive to variation of the nearby dihedral angle(s). Possible causes for the broad line width of the F signals of these membrane proteins are discussed.