(E)-4-(allyloxy)-2-methylbut-2-en-1-ol | 950191-96-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-4-(allyloxy)-2-methylbut-2-en-1-ol
• CAS: 950191-96-5
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: JGPXDVWMPWVPAR-XBXARRHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.13
• 重原子数：
  10.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (E)-4-(allyloxy)-2-methylbut-2-en-1-ol 、 乙酸酐 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 6.5h， 生成 (E)-4-(allyloxy)-2-methylbut-2-en-1-yl acetate
  参考文献：
  名称：

  Geminal Alkene–Alkyne Cross Metathesis Using a Relay Strategy

  摘要：

  A relay strategy was employed to achieve an intermolecular ene-yne metathesis between 1,1-disubstituted alkenes and alkynes. The relay serves to activate an unreactive alkene which will not participate in ene-yne metathesis. The new relay cross ene-yne metathesis gives rise to 1,1,3-trisubstituted-1,3-dienes previously inaccessible by direct ene-yne metathesis methods.

  DOI：

  10.1021/ol301846q
• 作为产物：
  描述：

  (E)-4-((tert-butyldimethylsilyl)oxy)-3-methylbut-2-en-1-ol 在 四丁基氟化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 5.5h， 生成 (E)-4-(allyloxy)-2-methylbut-2-en-1-ol
  参考文献：
  名称：

  Geminal Alkene–Alkyne Cross Metathesis Using a Relay Strategy

  摘要：

  A relay strategy was employed to achieve an intermolecular ene-yne metathesis between 1,1-disubstituted alkenes and alkynes. The relay serves to activate an unreactive alkene which will not participate in ene-yne metathesis. The new relay cross ene-yne metathesis gives rise to 1,1,3-trisubstituted-1,3-dienes previously inaccessible by direct ene-yne metathesis methods.

  DOI：

  10.1021/ol301846q

文献信息

• Exploiting Non-Covalent Interactions in Synthesis: Macrocyclization Employing Amide-Based Auxiliaries
  作者：Yassir El-Azizi、Joseph E. Zakarian、Lisa Bouillerand、Andreea R. Schmitzer、Shawn K. Collins

  DOI：10.1002/adsc.200800365

  日期：2008.10.6

  Efficient macrocyclic olefin and en-yne metathesis can be conducted employing benzyl ester auxiliaries that engage in quadrupolar interactions. The use of amide linkers in place of esters results in higher overall yields. Computational studies suggest that amide auxiliaries stabilize conformers conducive to macrocyclization over 22 times more efficiently than an ester linkage. Molecular modelling studies

  可以使用参与四极相互作用的苄基酯助剂进行有效的大环烯烃和烯炔复分解。使用酰胺连接基代替酯导致更高的总收率。计算研究表明，酰胺助剂可稳定有助于大环化的构象异构体，其效率是酯键的22倍以上。分子建模研究还表明，与酰胺类助剂所预测的孤对（lp）：π相互作用相反，酰胺类助剂更倾向于参与四极相互作用。
• Development of Perfluoroarene−Arene Interactions for Macrocyclic En-yne Metathesis and the Total Synthesis of Macrocyclic Natural Products
  作者：Shawn K. Collins、Yassir El-Azizi、Andreea R. Schmitzer

  DOI：10.1021/jo070568r

  日期：2007.8.1

  en-yne metathesis of strained macrocyclic systems is possible using highly active Grubbs−Hoveyda second-generation catalyst and when exploiting fluoroarene−arene gearing interactions. These interactions are effective even under high reaction temperatures and in the presence of a competitive π-rich solvent such as toluene. These results suggest that efficient π−π stacking or π−lp interactions between

  使用高活性的第二代Grubbs-Hoveyda催化剂以及利用氟代芳烃与芳烃的齿轮相互作用，可以有效地实现应变大环系统的直接烯炔复分解。这些相互作用甚至在高反应温度下和在竞争性的富含π的溶剂（如甲苯）的存在下也是有效的。这些结果表明，含有五氟苯基和3,5-双（三氟甲基）苯基的助剂之间有效的π-π堆积或π-lp相互作用是造成大环化产物产率高的原因。3,5-双（三氟甲基）苄基齿轮元件可提供更高的收率和更大的E在大环烯炔复分解中的选择性形成模型对环烷，可用于制备天然产物longithorone系列成员。
• Exploiting Quadrupolar Interactions in the Synthesis of the Macrocyclic Portion of Longithorone C
  作者：Joseph E. Zakarian、Yassir El-Azizi、Shawn K. Collins

  DOI：10.1021/ol800821f

  日期：2008.7.17

  2,3,4,5,6-Pentafluorobenzyl and 3,5-bistrifluoromethylbenzyl ester auxiliaries can enable difficult macrocyclizations to afford rigid all-carbon paracyclophanes. The effectiveness of these auxiliaries has been demonstrated in preparing the carbon skeleton of the macrocyclic natural product longithorone C.