(5R*,6S*)-5,6-bis(methoxymethyl)cyclohexa-1,3-diene | 142634-37-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (5R*,6S*)-5,6-bis(methoxymethyl)cyclohexa-1,3-diene
• 英文别名: 1,6-bis(methoxymethyl)cyclohex-2,4-diene；(5S,6R)-5,6-bis(methoxymethyl)cyclohexa-1,3-diene
• CAS: 142634-37-5
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: VJAUWSXFUKAXCG-AOOOYVTPSA-N

物化性质

• 沸点：
  209.7±13.0 °C(Predicted)
• 密度：
  0.929±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  exo-2,3-bis(methoxymethyl)-7-oxabicyclo[2.2.1]hept-5-ene 在 dimethyl(phenyl)silylcuprate 、 锂丁酯 作用下， 以 四氢呋喃 为溶剂， 以87%的产率得到(5R*,6S*)-5,6-bis(methoxymethyl)cyclohexa-1,3-diene
  参考文献：
  名称：

  An efficient synthesis of 1,3-cyclohexadienes from oxabicyclo[2.2.1]heptenes via tandem ring opening-Peterson elimination reactions

  摘要：

  Oxabicyclo[2.2.1]heptenes react with PhMe2SiLi or PhMe2SiCu.LiCN to yield 1,3-cyclohexadienes. The reaction pathway is shown to proceed via an addition-elimination-Peterson olefination sequence.

  DOI：

  10.1021/jo00041a003

文献信息

• Copper-Catalyzed Ring-Opening of Heterobicyclic Alkenes with Grignard Reagents: Remarkably High<i>anti</i>-Stereocontrol
  作者：Ramón Gómez Arrayás、Juan Carlos Carretero、Silvia Cabrera

  DOI：10.1055/s-2006-926379

  日期：——

  protocols for the ring-opening reaction of heterobicyclic alkenes with carbon nucleophiles which typically occur with syn selectivity, the alkylative ring-opening reaction of [2.2.1]oxa- and azabicyclic alkenes with Grignard reagents in the presence of a catalytic amount of copper(I) takes place with very high or complete anti-stereocontrol under smooth reaction conditions. This new procedure proved to

  与大多数报道的杂双环烯烃与碳亲核试剂的开环反应（通常以顺式选择性发生）不同，[2.2.1] 氧杂环和氮杂双环烯烃与格氏试剂的烷基化开环反应在催化量的铜 (I) 在平稳的反应条件下以非常高或完全的反立体控制发生。事实证明，这种新方法适用于格氏试剂和双环烯烃的范围很广。特别值得注意的是低反应性底物如非芳族氧杂双环烯烃和氮杂苯并降冰片二烯在该催化剂体系下的容易开环反应。
• Convenient Synthesis of meso-Cyclohexa-1,3-dienes by One-Pot Two-Step Deoxygenation of 7-Oxabicyclo[2.2.1]hept-2-enes
  作者：Ryo Irie、Tomotsugu Yano、Takashi Fujishima

  DOI：10.1055/s-0029-1218618

  日期：2010.3

  Iron(III) hydroxide oxide was found to be an efficient catalyst for the ring-opening reaction of 5,6-cis-disubstituted 7-oxa­bicyclo[2.2.1]hept-2-enes with acetyl bromide in dichloromethane at room temperature to give cyclohexene derivatives with leaving groups (acetoxy or bromo groups) disposed on each allylic position. A successive one-pot treatment of the reaction mixture with zinc powder and tetrahydrofuran

  发现氢氧化铁（III）是5,6-顺式二取代的7-氧杂双环[2.2.1]庚-2-烯与乙酰溴在室温下在二氯甲烷中进行开环反应的有效催化剂，得到在每个烯丙基位置上带有离去基团（乙酰氧基或溴基）的环己烯衍生物。用锌粉和四氢呋喃对反应混合物进行连续的一锅法处理成功地诱导了还原性1，4-消除，以高到高的产率提供了合成上有用的5，6-二取代的内消旋-环己-1，3-二烯。 催化-开环-呋喃-还原-消除-环己二烯
• Copper-Catalyzed Anti-Stereocontrolled Ring Opening of Oxabicyclic Alkenes with Grignard Reagents
  作者：Ramón Gómez Arrayás、Silvia Cabrera、Juan C. Carretero

  DOI：10.1021/ol034283m

  日期：2003.4.1

  [reaction: see text] A general copper-catalyzed procedure for the stereoselective ring opening of [2.2.1]-oxabicyclic alkenes with Grignard reagents is described. In the presence of catalytic amounts of CuCl/PPh(3) the reaction occurs with very high or complete anti selectivity in all cases.

  [反应：见正文]描述了用格氏试剂对[2.2.1]-氧杂双环烯烃的立体选择性开环的一般铜催化方法。在催化量的CuCl / PPh（3）存在下，反应在所有情况下均具有很高或完全的反选择性。
• Iron-Catalyzed Regio- and Stereoselective Ring Opening of [2.2.1]- and [3.2.1]Oxabicyclic Alkenes with a Grignard Reagent
  作者：Masaharu Nakamura、Keiko Matsuo、Toshihiro Inoue、Eiichi Nakamura

  DOI：10.1021/ol034375b

  日期：2003.4.1

  [reaction: see text] Arylative and alkenylative ring-opening reactions of a [2.2.1]- or [3.2.1]oxabicyclic alkene with a Grignard reagent take place in the presence of a catalytic amount of iron(III) chloride and a stoichiometric amount of TMEDA to produce a highly substituted 3-cyclohexen-1-ol or 3-cyclohepten-1-ol in good yield with high regio- and stereoselectivity.

  [反应：参见正文] [2.2.1]-或[3.2.1]氧杂双环烯烃与格利雅试剂的芳基和烯基开环反应是在催化量的氯化铁（III）和氯化氢存在下进行的。化学计量的TMEDA量，可产生高取代度的3-环己烯-1-醇或3-环庚烯-1-醇，并具有较高的区域选择性和立体选择性。