(E)-1-(3,3,4,4,5,5,6,6,6-nonafluoro-hexen-1-yl)-naphtalene | 1374105-08-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (E)-1-(3,3,4,4,5,5,6,6,6-nonafluoro-hexen-1-yl)-naphtalene
• 英文别名: (E)-1-(3,3,4,4,5,5,6,6,6-nonafluorohex-1-en-1-yl)naphthalene；(E)-1-(3,3,4,4,5,5,6,6,6-nonafluorohexen-1-yl)naphthalene
• CAS: 1374105-08-4
• 化学式: C₁₆H₉F₉
• 分子量: 372.233
• InChiKey: MXWDKOQORUZFPJ-CMDGGOBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.32
• 重原子数：
  25.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  1,3-bis(1-iodo-3,3,4,4,5,5,6,6,6-nonafluorohexan-1-yl)tetramethyldisiloxane 在 三氟化硼乙醚 、 四丁基氟化铵 、 palladium diacetate 、 二乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 132.0h， 生成 (E)-1-(3,3,4,4,5,5,6,6,6-nonafluoro-hexen-1-yl)-naphtalene
  参考文献：
  名称：

  Hiyama coupling reaction of fluorous alkenyl-fluorosilanes: Scope and mechanistic considerations

  摘要：

  Novel fluorous alkenyl-fluorosilanes (CnF2n+1CH=CHSiMe2F; n = 4, 6, 8; 5a-c) were synthetized in a three step procedure from perfluoroalkyliodides and dimethylvinylchlorosilane. They were first reacted with iodobenzene at room temperature in Hiyama coupling reaction (DMF, Pd(OAc)(2), TBAF, 72 h) to afford the appropriate omega-perfluoroalkyl-styrenes (CnF2n+1CH=CHC6H5, n = 4, 6, 8): then the reactivity of 5a with monosubstituted iodobenzenes was studied. The coupling reaction of Sa with o-substituted iodobenzenes usually failed, while that of with the m- and p-substituted ones gave fluorous styrenes [m- or p-(C4F9CH=CH)C6H4X], independently of the electronic effect of their substituent (X = Br, CF3, CH3, OCH3). These volatile products can easily be isolated by steam-distilltaion and purified further by distillation. The mechanism of the above coupling reactions was a pure Hiyama type involving fluoride-ion induced transmetallation without any Heck type contribution, since no coupling product of C6F13CH=CH2 and C6H5I was observed in blank control experiments using similar conditions (DMF, TBAF, Pd(OAc)(2), 72 h, 25 degrees C). (c) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2012.03.007

文献信息

• Fluoroalkenylation of boronic acids <i>via</i> an oxidative Heck reaction
  作者：Da Seul Lee、Eun Jin Cho

  DOI：10.1039/c9ob00332k

  日期：——

  A fluoroalkenylation of boronic acids with fluoroalkyl alkenes has been developed. The Pd-catalyzed oxidative Heck coupling reaction proceeds under an oxygen atmosphere at room temperature, in the absence of a base and/or a ligand, showing excellent practicality of the process. This simple transformation is highly stereoselective to provide only E-isomers. In addition to the general approach using

  已经开发了用氟代烷基烯烃对硼酸的氟代烯基化。Pd催化的氧化Heck偶联反应是在室温下在氧气气氛下，在没有碱和/或配体的情况下进行的，显示了该方法的极好的实用性。这种简单的转化是高度立体选择性的，仅提供E-异构体。除了将烯烃与官能化的氟代烷基试剂一起使用的一般方法外，该方法还通过将芳香族体系转移至缺电子的氟代烷基烯烃上，提供了一种有效的替代方法来生产有价值的有机氟。
• Siloxane based syntheses of fluorous ethenes and their tandem Heck reactions with aryl iodides
  作者：Ágnes Csapó、József Rábai

  DOI：10.1016/j.jfluchem.2012.07.010

  日期：2012.12

  Perfluoroalkyl-ethenes (RfnCH=CH2, 6a-c; a, n = 4; b, n = 6; c, n = 8) were prepared in good isolated yields (67-89%) and high purity (GC assay > 98%) from various fluorinated organosilanes in fluoride-anion assisted protodesilylation reactions. The environmentally more benign 'KF/NEt3/H2O' reagent combination introduced here was found as an effective substitute for the commonly used tetrabutylammonium-fluoride trihydrate (TBAF center dot 3H(2)O) as a fluoride source. Fluorous styrenes ((E)-RfnCH=CH-Ar, 8) were then prepared in good isolated yields (58-93%/iodoarene) and purities (GC assay > 95%) with the Pd(0) catalyzed Heck coupling of iodoarenes (Ar-1, 7) and perfluoroalkyl-ethenes generated in situ by the fluoride assisted cleavage of (beta-perfluoroalkyl-alpha-iodo-ethyl)-siloxane ((RfnCH2CH(I)SiMe2](2)O, 3) precursors in DMF solution at elevated temperatures. They are accessible by the one-pot reaction of dimethylvinylchlorosilane (CH2=CHSiMe2Cl, 2) and perfluoroalkyl iodides (R-I, 1) as we reported earlier. Similarly, the radical chain addition of C8F17I to CH2=CHSi(OMe)(3) (9) gave (beta-perfluorooctyl-alpha-iodo-ethyl)-trimethoxysilane ([C8F17CH2CH(I)]Si(OMe)(3), 10) in good yield, which then was reacted with silica gel in dry toluene to obtain an SiO2-bonded (perfluorooctyl)ethene surrogate [silica(-O-)(3)Si-CH(I)CH2C8F17, 11]. The fluoride assisted cleavage of 11 and tandem Heck reaction with iodobenzene afforded the appropriate cross-coupled product (E)-C8F17CH=CHPh. (C) 2012 Elsevier B.V. All rights reserved.