(E)-2-(2,6,6-trimethylcyclohexen-1-yl)-ethenyl (trifluoromethyl)sulfonate | 303779-99-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (E)-2-(2,6,6-trimethylcyclohexen-1-yl)-ethenyl (trifluoromethyl)sulfonate
• 英文别名: (E)-2-(2,2,6-trimethylcyclohexen-1-yl)ethenyl trifluoromethanesulfonate；[(E)-2-(2,6,6-trimethylcyclohexen-1-yl)ethenyl] trifluoromethanesulfonate
• CAS: 303779-99-9
• 化学式: C₁₂H₁₇F₃O₃S
• 分子量: 298.326
• InChiKey: JBAMWTZSRCJMEW-SOFGYWHQSA-N

物化性质

• 沸点：
  319.7±42.0 °C(Predicted)
• 密度：
  1.275±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (E)-2-(2,6,6-trimethylcyclohexen-1-yl)-ethenyl (trifluoromethyl)sulfonate 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex N,N-二甲基丙烯基脲 、 manganese(IV) oxide 、 氢氧化钾 、 正丁基锂 、 三苯胂 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 11.5h， 生成 13-demethyl all-trans-retinoic acid
  参考文献：
  名称：

  Preparation and biological activity of 13-substituted retinoic acids

  摘要：

  13-Demethyl or 13-substituted all-E- and 9Z-retinoic acids were synthesized using a palladium-catalyzed coupling reaction of enol triflates and tributylstannylolefins. Their biological activities were then measured. The 13-ethyl analogs exhibited approximately one-half of the antiproliferative and differentiation-inducing activity of ATRA in HL-60 cells. In contrast, in the 9Z-derivatives, all analogs, except for the 13-butyl derivatives, showed apoptosis-inducing activity. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2004.04.047
• 作为产物：
  描述：

  2,6,6-三甲基-1-环己烯基乙醛 、 phenylbis[(trifluoromethyl)sulfonyl]amine 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以73%的产率得到(E)-2-(2,6,6-trimethylcyclohexen-1-yl)-ethenyl (trifluoromethyl)sulfonate
  参考文献：
  名称：

  Caesium fluoride-promoted Stille coupling reaction: an efficient synthesis of 9Z-retinoic acid and its analogues using a practical building block

  摘要：

  通过氟化铯促进的Stille偶联反应，成功实现了9Z-维甲酸的高效快速全合成；利用常见的构建模块，通过同一方法，无需Z双键的异构化，也制备了9Z-维甲酸类似物。

  DOI：

  10.1039/b813760a

文献信息

• Synthesis of 9Z-9-Substituted Retinoic Acids by Palladium Catalyzed Coupling Reaction of a Vinyl Triflate with Alkenyl Stannanes.
  作者：Akimori WADA、Yuki NOMOTO、Kenji TANO、Eriko YAMASHITA、Masayoshi ITO

  DOI：10.1248/cpb.48.1391

  日期：——

  Palladium catalyzed cross coupling reactions of a vinyl triflate intermediate and various alkenyl stananes afforded trisubstituted Z-olefins stereoselectively in high yields. These olefins were then converted to the corresponding 9Z-retinoic acids via Horner-Emmons reaction and subsequent basic hydrolysis in excellent yields.

  钯催化的乙烯基三氟磺酸酯中间体与各种烯基锡烷的交叉耦合反应，以高产率立体选择性地合成了三取代的Z型烯烃。随后通过Horner-Emmons反应和后续的碱性水解，这些烯烃以极佳的产率转化为相应的9Z型维甲酸。
• Palladium-Catalyzed Coupling Reaction of an Enol Nonaflate with (Vinyl)tributylstannanes and Acetylenes: A Highly Stereoselective Synthesis of 8,18-¹³C₂-Labeled Retinal
  作者：Akimori Wada、Yasuhiro Ieki、Saeko Nakamura、Masayoshi Ito

  DOI：10.1055/s-2005-865294

  日期：——

  Here we report that enol nonaflates exhibit higher reactivity than the corresponding enol triflates in palladium-catalyzed cross-coupling reactions with various (vinyl)tributylstannanes and acetylenes. We also highlight the reaction of a vinyl nonaflate, containing two 1 3 C-labeled carbon atoms with an alkenyl stannane, which afforded the trisubstituted E-olefin stereoselectively in high yield. The

  在这里，我们报告烯醇九氟甲磺酸酯在钯催化的与各种（乙烯基）三丁基锡烷和乙炔的交叉偶联反应中表现出比相应的烯醇三氟甲磺酸酯更高的反应性。我们还强调了含有两个 1 3 C 标记的碳原子的乙烯基九烷基锡与烯基锡烷的反应，它以高产率立体选择性地提供了三取代的 E-烯烃。然后将 E-烯烃转化为相应的全 E-视黄醛。
• Palladium Catalyzed Coupling Reaction of an Enol Nonaflate with (Vinyl)tributylstannanes and Acetylenes
  作者：Akimori Wada、Yasuhiro Ieki、Masayoshi Ito

  DOI：10.1055/s-2002-32602

  日期：——

  stereoselective synthesis of trienes and dienynes was developed by palladium catalyzed cross coupling reactions of an enol nonaflate with (vinyl)tributylstannanes and acetylenes in good to excellent yields. Here, the enol nonaflate exhibited a higher reactivity compared with the corresponding enol triflate in the coupling reactions.

  通过钯催化烯醇壬酯与（乙烯基）三丁基锡烷和乙炔的交叉偶联反应，开发了一种立体选择性合成三烯和二炔的新方法，收率良好至极好。在这里，与相应的烯醇三氟甲磺酸酯相比，烯醇九氟甲磺酸酯在偶联反应中表现出更高的反应性。
• Caesium fluoride-promoted Stille coupling reaction: an efficient synthesis of 9Z-retinoic acid and its analogues using a practical building block
  作者：Takashi Okitsu、Kinya Iwatsuka、Akimori Wada

  DOI：10.1039/b813760a

  日期：——

  A highly efficient and rapid total synthesis of 9Z-retinoic acid was accomplished by caesium fluoride-promoted Stille coupling reaction; using a common building block, 9Z-retinoic acid analogues were also prepared by the same method without isomerisation of the Z-double bond.

  通过氟化铯促进的Stille偶联反应，成功实现了9Z-维甲酸的高效快速全合成；利用常见的构建模块，通过同一方法，无需Z双键的异构化，也制备了9Z-维甲酸类似物。
• Preparation and biological activity of 13-substituted retinoic acids
  作者：Akimori Wada、Kouki Fukunaga、Masayoshi Ito、Yukari Mizuguchi、Kimie Nakagawa、Toshio Okano

  DOI：10.1016/j.bmc.2004.04.047

  日期：2004.7

  13-Demethyl or 13-substituted all-E- and 9Z-retinoic acids were synthesized using a palladium-catalyzed coupling reaction of enol triflates and tributylstannylolefins. Their biological activities were then measured. The 13-ethyl analogs exhibited approximately one-half of the antiproliferative and differentiation-inducing activity of ATRA in HL-60 cells. In contrast, in the 9Z-derivatives, all analogs, except for the 13-butyl derivatives, showed apoptosis-inducing activity. (C) 2004 Elsevier Ltd. All rights reserved.