2,3-epoxy-1-difluoromethylidene-3,5,5-trimethylcyclohexane | 512780-63-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: 2,3-epoxy-1-difluoromethylidene-3,5,5-trimethylcyclohexane
• 英文别名: 5-(Difluoromethylidene)-1,3,3-trimethyl-7-oxabicyclo[4.1.0]heptane；5-(difluoromethylidene)-1,3,3-trimethyl-7-oxabicyclo[4.1.0]heptane
• CAS: 512780-63-1
• 化学式: C₁₀H₁₄F₂O
• 分子量: 188.217
• InChiKey: BOZZKFUBJGDFAN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  2,3-epoxy-1-difluoromethylidene-3,5,5-trimethylcyclohexane 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23%的产率得到3-(difluoromethyl)-1,3,5-trimethylcyclohex-2-enol
  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：

  异佛尔酮 、 alkaline earth salt of/the/ methylsulfuric acid 在 六甲基磷酰三胺 、 sodium hydroxide 、 双氧水 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 6.0h， 生成 2,3-epoxy-1-difluoromethylidene-3,5,5-trimethylcyclohexane
  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

• Preparation and regioselective reactions of novel gem-difluorinated vinyloxiranes with some organometallic reagents
  作者：Takashi Yamazaki、Hisanori Ueki、Tomoya Kitazume

  DOI：10.1039/b208981e

  日期：2002.11.4

  Hitherto unknown, relatively labile gem-difluorinated vinyloxiranes were prepared by difluoro-Wittig reactions with alpha,beta-epoxyketones; for these vinyloxiranes alkyl groups were delivered at the fluorine-attached terminal carbon atom in an SN2' manner by RLi, while Me3Al and MeMgBr-CuCl (3: 1) introduced the Me group at the allylic epoxy carbon with retention and inversion of the original stereochemistry

  迄今未知的，相对不稳定的宝石-二氟乙烯基环氧乙烷是通过与α，β-环氧酮的二氟-维蒂希反应制备的；这些乙烯基氧杂环戊烷的烷基基团是通过RLi以SN2'方式在附有氟的末端碳原子上传递的，而Me3Al和MeMgBr-CuCl（3：1）在烯丙基环氧碳上引入了Me基团，保留并反转了原始分别为立体化学。
• 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。
• 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.