3,3-dimethyl-6-methoxy-(E,Z)-5-hexen-1-ol | 358351-20-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 3,3-dimethyl-6-methoxy-(E,Z)-5-hexen-1-ol
• 英文别名: 1-(methoxy)-4,4-dimethyl-1-en-hexan-6-ol；6-methoxy-3,3-dimethylhex-5-en-1-ol
• CAS: 358351-20-9
• 化学式: C₉H₁₈O₂
• 分子量: 158.241
• InChiKey: YWDCMBOWSXPAPV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.95
• 重原子数：
  11.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  3,3-dimethyl-6-methoxy-(E,Z)-5-hexen-1-ol 在 正丁基锂 、 草酰氯 、 二甲基亚砜 、 三乙胺 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 21.42h， 生成 1,7-dimethoxy-4,4-dimethyl-(E,Z)-1,6-octadiene
  参考文献：
  名称：

  Intramolecular Anodic Olefin Coupling Reactions: A New Approach to the Synthesis of Angularly Fused, Tricyclic Enones

  摘要：

  A number of intramolecular anodic olefin coupling reactions have been examined in order to determine the feasibility of using a sequential electrochemical oxidation-aldol condensation approach for constructing polycyclic enones. Initially, substrates comprised of an aldehyde enol ether tethered to a ketone enol ether were examined. In a model study, it was shown that such a substrate could lead to a successful electrochemical oxidation-aldol condensation sequence. However, the difficulties associated with both the synthesis and the poor stability of the ketone enol ethers greatly reduced the potential utility of this approach. This problem was circumvented by taking advantage of the compatibility of allylsilane groups with the electrolysis reaction. In these examples, ozonolysis of the electrochemical cyclization product afforded the 1,4-dicarbonyl substrate needed for the aldol condensation. The use of the less reactive allylsilane group in the electrochemical reaction still allowed for the construction of quaternary carbons. Finally a pair of angularly fused, tricyclic enones were synthesized. The regiochemistry of the enone in the product could be controlled by the proper choice of the substrate for the electrolysis and manipulation of the resulting cyclized product.

  DOI：

  10.1021/jo00088a019
• 作为产物：
  描述：

  4,4-dimethyltetrahydro-2H-pyran-2-ol 、 甲氧基甲基三苯基氯化膦 在 正丁基锂 作用下， 生成 3,3-dimethyl-6-methoxy-(E,Z)-5-hexen-1-ol
  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

• Anodic oxidations of electron-rich olefins: radical cation based approaches to the synthesis of bridged bicyclic ring skeletons
  作者：S.Hari Krishna Reddy、Kazuhiro Chiba、Yongmao Sun、Kevin D Moeller

  DOI：10.1016/s0040-4020(01)00358-1

  日期：2001.6

  intramolecular anodic olefin coupling reactions for building bicyclo[3.2.1]octane ring skeletons has been examined. While simple model systems using bis enol ether substrates readily led to the formation of bicyclic products, application of the reactions to total synthesis efforts were hindered by reactions forming dimethoxy acetal groups at both the terminating and initiating ends of the cyclization reactions

  已经研究了分子内阳极烯烃偶联反应在构建双环[3.2.1]辛烷环骨架中的应用。尽管使用双烯醇醚底物的简单模型系统容易导致双环产物的形成，但是由于在环化反应的末端和起始端均形成二甲氧基缩醛基团的反应阻碍了该反应在全合成工作中的应用。为了解决该问题，已经研究了基于乙烯酮缩醛的引发基团。烯酮二硫缩醛基的使用被证明对于该目的特别有用。
• Intramolecular anodic olefin coupling reactions: the use of bis enol ether substrates
  作者：Kevin D. Moeller、Luzviminda V. Tinao

  DOI：10.1021/ja00029a036

  日期：1992.1

  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.
• Intramolecular Anodic Olefin Coupling Reactions: A New Approach to the Synthesis of Angularly Fused, Tricyclic Enones
  作者：Luzviminda V. Tinao-Wooldridge、Kevin D. Moeller、Christine M. Hudson

  DOI：10.1021/jo00088a019

  日期：1994.5

  A number of intramolecular anodic olefin coupling reactions have been examined in order to determine the feasibility of using a sequential electrochemical oxidation-aldol condensation approach for constructing polycyclic enones. Initially, substrates comprised of an aldehyde enol ether tethered to a ketone enol ether were examined. In a model study, it was shown that such a substrate could lead to a successful electrochemical oxidation-aldol condensation sequence. However, the difficulties associated with both the synthesis and the poor stability of the ketone enol ethers greatly reduced the potential utility of this approach. This problem was circumvented by taking advantage of the compatibility of allylsilane groups with the electrolysis reaction. In these examples, ozonolysis of the electrochemical cyclization product afforded the 1,4-dicarbonyl substrate needed for the aldol condensation. The use of the less reactive allylsilane group in the electrochemical reaction still allowed for the construction of quaternary carbons. Finally a pair of angularly fused, tricyclic enones were synthesized. The regiochemistry of the enone in the product could be controlled by the proper choice of the substrate for the electrolysis and manipulation of the resulting cyclized product.