(E)-3,4-epoxy-1,1-difluoro-2-methyl-4-(4-methylphenyl)but-1-ene

• 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: (E)-3,4-epoxy-1,1-difluoro-2-methyl-4-(4-methylphenyl)but-1-ene
• 英文别名: (2R,3R)-2-(1,1-Difluoro-1-propen-2-yl)-3-(4-methylphenyl)oxirane；(2R,3R)-2-(1,1-difluoroprop-1-en-2-yl)-3-(4-methylphenyl)oxirane
• 化学式: C₁₂H₁₂F₂O
• 分子量: 210.223
• InChiKey: MHYMSOWTNDWCCM-GHMZBOCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-3,4-epoxy-1,1-difluoro-2-methyl-4-(4-methylphenyl)but-1-ene 在 硼烷四氢呋喃络合物 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以85%的产率得到(Z)-4,4-difluoro-3-methyl-1-(4-methylphenyl)but-2-en-1-ol
  参考文献：
  名称：

  Synthesis of Trifluoro- or Difluoromethylated Olefins by Regio- and Stereocontrolled S_N2‘ Reactions of gem-Difluorinated Vinyloxiranes

  摘要：

  This paper presents a highly stereoselective synthesis of trifluoro- or difluoromethylated olefins via an S(N)2' type fluorination or reductions of gem-difluorinated vinyloxiranes. Their fluorination with HF-Py furnished trifluoromethylated allylic alcohols with exclusive E selectivity. On the other hand, their reduction with DIBAL-H afforded difluoromethylated E-allylic alcohols predominantly, whereas the corresponding Z isomers were formed exclusively by treatment with BH(3)center dot THF.

  DOI：

  10.1021/jo060089c
• 作为产物：
  描述：

  4-甲基亚苄基丙酮 在 六甲基磷酰三胺 、 sodium hydroxide 、 双氧水 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 3.5h， 生成 (E)-3,4-epoxy-1,1-difluoro-2-methyl-4-(4-methylphenyl)but-1-ene
  参考文献：
  名称：

  制备和区域选择性小号Ñ 2'小说的反应克EM与RLi的-Difluorinated Vinyloxiranes

  摘要：

  从容易获得的α，β-环氧酮制备了一系列迄今未知的3,4-环氧-1,1-二氟丁烯，发现这些化合物发生了区域选择性S N 2'反应，并在高度阳性时与硬RLi亲核试剂发生反应。与仅具有低区域选择性的相应非氟化乙烯基氧杂环戊烷的情况形成鲜明对比的是，带电末端具有氟的sp 2碳原子形成鲜明的对比。HMPA的加入大大改善了产物的烯属立体选择性。理论计算被用来定性地探索这些反应中选择性的性质。

  DOI：

  10.1021/jo049025x

文献信息

• Regio- and Stereoselective Reactions of <i>g</i><i>em</i>-Difluorinated Vinyloxiranes with Heteronucleophiles
  作者：Hisanori Ueki、Tomoya Kitazume

  DOI：10.1021/jo051468t

  日期：2005.11.1

  Regio- and stereoselectivity in reactions of gem-difluorinated vinyloxiranes with heteronucleophiles were successfully controlled. Halogen atoms were introduced regioselectively at the allylic epoxide carbon with an inversion in stereochemistry using MgBr2·Et2O or Li2CuCl4 to produce anti-vic-halohydrine. The other diastereomers were obtained selectively using LiBr/AcOH or BCl3, and SN2‘ type products

  宝石-二氟乙烯基环氧乙烷与杂多亲核试剂反应的区域选择性和立体选择性已得到成功控制。卤原子物在使用MgBr在立体化学的反转烯丙基环氧碳区域选择性地引入2 ·的Et 2 O或栗2的CuCl 4，以产生抗- VIC -halohydrine。使用LiBr / AcOH或BCl 3选择性地获得其他非对映异构体，并且通过改变反应温度以优异的E偏爱选择性地形成S N 2'型产物。此外，进一步的研究使我们发现区域和立体选择性S几种布朗斯台德酸的N 2'加入取决于酸的p K a值。在强酸性条件下，我们完全获得Ë烯丙醇。
• Highly regio- and stereocontrolled brominations of gem-difluorinated vinyloxiranes
  作者：Hisanori Ueki、Tomoya Kitazume

  DOI：10.1016/j.tetlet.2005.06.071

  日期：2005.8

  gem-Difluorinated vinyloxiranes, which are useful synthetic intermediates for difluorinated compounds, were brominated regio- and stereoselectively. Introduction of bromide at the allylic epoxide carbon with inversion of stereochemistry was realized by MgBr2·Et2O to furnish an anti vic-bromohydrine, whereas the reaction with LiBr/AcOH afforded the other diastereomer selectively. Moreover, both reactions at high

  将对二氟化合物有用的合成中间体宝石-二氟乙烯基氧杂环丁烷进行区域和立体选择性的溴化。MgBr 2 ·Et 2 O实现了溴化物在烯丙基环氧碳上的立体化学转化，从而提供了一种抗vic-溴代醇，而与LiBr / AcOH的反应则选择性地提供了另一种非对映异构体。而且，在高温下的两个反应均允许主要获得热力学上有利的产物E-烯丙基醇。
• Preparation and Regioselective S_N2‘ Reaction of Novel <i>g</i><i>em</i>-Difluorinated Vinyloxiranes with RLi
  作者：Hisanori Ueki、Takashi Chiba、Takashi Yamazaki、Tomoya Kitazume

  DOI：10.1021/jo049025x

  日期：2004.10.1

  β-epoxy ketones and these compounds were found to undergo regioselective SN2‘ reactions with hard RLi nucleophiles occurring at the highly positively charged terminal fluorine-possessing sp2 carbon atom in quite sharp contrast to the cases of the corresponding nonfluorinated vinyloxiranes which only attained a low level of regioselectivity. Addition of HMPA substantially improved the products' olefinic

  从容易获得的α，β-环氧酮制备了一系列迄今未知的3,4-环氧-1,1-二氟丁烯，发现这些化合物发生了区域选择性S N 2'反应，并在高度阳性时与硬RLi亲核试剂发生反应。与仅具有低区域选择性的相应非氟化乙烯基氧杂环戊烷的情况形成鲜明对比的是，带电末端具有氟的sp 2碳原子形成鲜明的对比。HMPA的加入大大改善了产物的烯属立体选择性。理论计算被用来定性地探索这些反应中选择性的性质。
• Synthesis of Trifluoro- or Difluoromethylated Olefins by Regio- and Stereocontrolled S_N2‘ Reactions of <i>gem</i>-Difluorinated Vinyloxiranes
  作者：Hisanori Ueki、Takashi Chiba、Tomoya Kitazume

  DOI：10.1021/jo060089c

  日期：2006.4.1

  This paper presents a highly stereoselective synthesis of trifluoro- or difluoromethylated olefins via an S(N)2' type fluorination or reductions of gem-difluorinated vinyloxiranes. Their fluorination with HF-Py furnished trifluoromethylated allylic alcohols with exclusive E selectivity. On the other hand, their reduction with DIBAL-H afforded difluoromethylated E-allylic alcohols predominantly, whereas the corresponding Z isomers were formed exclusively by treatment with BH(3)center dot THF.