6-Methoxy-5-hexen-1-al (cis/trans) | 24281-36-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-Methoxy-5-hexen-1-al (cis/trans)
• 英文别名: 6-Methoxy-hex-5-enal；6-methoxyhex-5-enal
• CAS: 24281-36-5
• 化学式: C₇H₁₂O₂
• 分子量: 128.171
• InChiKey: SDAUGFHHJWCUIH-UHFFFAOYSA-N

物化性质

• 沸点：
  92.5-94.5 °C(Press: 25 Torr)
• 密度：
  0.951 g/cm3(Temp: 240 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  9
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6-Methoxy-5-hexen-1-al (cis/trans) 在 2,6-二甲基吡啶 、 叔丁基锂 、 lithium perchlorate 作用下， 以 乙腈 为溶剂， 反应 21.0h， 生成 cis-1,2-bis(dimethoxymethyl)cyclopentane
  参考文献：
  名称：

  Intramolecular anodic olefin coupling reactions: the use of bis enol ether substrates

  摘要：

  In an effort to develop electrochemical methods for directly initiating oxidative cyclization reactions, the anodic oxidation of bis enol ether substrates has been examined. The reactions were found to lead to the formation of five-, six-, and seven-membered-ring 1,4-dicarbonyl equivalents. The reactions were not found to be useful for generating larger ring sizes. Both alkyl and silyl enol ether substrates were found to be compatible with the conditions required for carbon-carbon bond formation. Cyclic voltammetry studies indicated that the cyclizations were fast and that the reactions happened at or near the electrode surface. Finally, the cyclization reactions were shown to be compatible with the formation of quaternary carbons, even when carbon-carbon bond formation involved the generation of two vicinal quaternary carbons.

  DOI：

  10.1021/ja00029a036
• 作为产物：
  描述：

  tetrahydro-2H-2-pyranol 在 正丁基锂 、 草酰氯 、 二甲基亚砜 作用下， 以 四氢呋喃 为溶剂， 反应 20.83h， 生成 6-Methoxy-5-hexen-1-al (cis/trans)
  参考文献：
  名称：

  Intramolecular anodic olefin coupling reactions: the use of bis enol ether substrates

  摘要：

  In an effort to develop electrochemical methods for directly initiating oxidative cyclization reactions, the anodic oxidation of bis enol ether substrates has been examined. The reactions were found to lead to the formation of five-, six-, and seven-membered-ring 1,4-dicarbonyl equivalents. The reactions were not found to be useful for generating larger ring sizes. Both alkyl and silyl enol ether substrates were found to be compatible with the conditions required for carbon-carbon bond formation. Cyclic voltammetry studies indicated that the cyclizations were fast and that the reactions happened at or near the electrode surface. Finally, the cyclization reactions were shown to be compatible with the formation of quaternary carbons, even when carbon-carbon bond formation involved the generation of two vicinal quaternary carbons.

  DOI：

  10.1021/ja00029a036

文献信息

• Oxidative Cyclization Based on Reversing the Polarity of Enol Ethers and Ketene Dithioacetals. Construction of a Tetrahydrofuran Ring and Application to the Synthesis of (+)-Nemorensic Acid
  作者：Bin Liu、Shengquan Duan、Angela C. Sutterer、Kevin D. Moeller

  DOI：10.1021/ja026739l

  日期：2002.8.1

  trapping group. The stereochemical outcome of cyclization reactions originating from the oxidation of an enol ether was found to be controlled by stereoelectronic factors. The utility of these cyclization reactions was illustrated with the synthesis of a key tetrahydrofuran building block for the synthesis of linalool oxide and rotundisine. Cyclization reactions triggered by the oxidation of a ketene dithioacetal

  已经研究了氧化环化反应用于构建四氢呋喃环的效用。在这些实验中，发现醇亲核试剂对于由烯醇醚和烯酮二硫缩醛基团生成的自由基阳离子中间体是有效的陷阱。醇捕获基团的反应性似乎介于烯醇醚和烯丙基硅烷捕获基团的反应性之间。发现源自烯醇醚氧化的环化反应的立体化学结果受立体电子因素控制。这些环化反应的效用通过合成芳樟醇氧化物和轮地辛的关键四氢呋喃结构单元来说明。由乙烯酮二硫缩醛氧化引发的环化反应导致更高水平的立体选择性。这些反应的立体化学结果表明是由涉及较大乙烯酮缩醛基团的空间因素引起的。通过完成 (+)-nemorensic 酸的不对称合成，证明了利用乙烯酮二硫缩醛衍生的自由基阳离子进行环化的合成效用。最后，这些反应被证明与酰胺亲核试剂的使用和内酯产物的直接形成相容。