(E)-3,4-epoxy-1,1-difluoro-2,4-diphenylbut-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-2,4-diphenylbut-1-ene
• 英文别名: (2R,3R)-2-(2,2-difluoro-1-phenylethenyl)-3-phenyloxirane
• 化学式: C₁₆H₁₂F₂O
• 分子量: 258.267
• InChiKey: TVKNHPPYWVKZCW-HUUCEWRRSA-N

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：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 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-2,4-diphenylbut-1-ene 在 氟化氢吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以53%的产率得到(E)-4,4,4-trifluoro-1,3-diphenylbut-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：

  (2S,3R)-2,3-epoxy-1,3-diphenylpropan-1-one 、 二溴二氟甲烷 在 六甲基磷酰三胺 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以97%的产率得到(E)-3,4-epoxy-1,1-difluoro-2,4-diphenylbut-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

• Highly regio- and stereocontrolled SN2′ reactions of gem-difluorinated vinyloxiranes with monoalkylcopper reagents
  作者：Hisanori Ueki、Takashi Chiba、Takashi Yamazaki、Tomoya Kitazume

  DOI：10.1016/j.tet.2005.09.018

  日期：2005.11

  Reaction of gem-difluorinated vinyloxiranes with RCu(X)Li allowed us to introduce the R group regioselectively at the fluorine-attached terminal carbon atom in an SN2′ manner to afford (E)-allylic alcohols exclusively, while homoallylic alcohols with anti stereochemical relationship were found to be obtained selectively from higher-ordered cuprates derived from CuCl and RMgBr in a ratio of 1:3.

  的反应宝石-difluorinated vinyloxiranes与RCU（X）栗允许我们在一个S的氟附着末端碳原子区域选择性地引入R基团Ñ 2'的方式，得到（ë） -烯丙基醇排他地，而高烯丙基醇与抗立体化学关系被发现是从高比重的CuCl和RMgBr以1：3的比例得到的。
• 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。
• Regio- and Stereoselective Reductions of <i>g</i><i>em</i>-Difluorinated Vinyloxiranes
  作者：Hisanori Ueki、Takashi Chiba、Tomoya Kitazume

  DOI：10.1021/ol050173z

  日期：2005.3.1

  synthesis of fluorinated compounds. Investigations of their reactions with nucleophiles resulted in highly regio- and stereoselective reductions. In their reactions with LiAlH4, hydride reacted at the allylic epoxide carbon to produce homoallylic alcohols exclusively. Moreover, regio- and stereoselective S(N)2' reactions were observed with DIBAL-H and BH3 x THF; the former afforded E allylic alcohols

  [反应：请参阅文本]宝石-二氟乙烯基氧杂环丁烷是合成氟化化合物的多功能构建基块。对它们与亲核试剂反应的研究导致了高度的区域选择性和立体选择性的降低。在与LiAlH4的反应中，氢化物在烯丙基环氧碳上反应，仅生成均烯丙基醇。此外，在DIBAL-H和BH3 x THF中观察到区域选择性和立体选择性S（N）2'反应。前者提供了E烯丙基醇，而后者则提供了具有出色选择性的相应Z异构体。
• 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.