(E and Z)-2-(dimethyl-(2-methyl-1-propenyl)siloxy)-1-(methoxymethylidene)cyclohexane | 149902-38-5

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (E and Z)-2-(dimethyl-(2-methyl-1-propenyl)siloxy)-1-(methoxymethylidene)cyclohexane
• 英文别名: [2-(methoxymethylidene)cyclohexyl]oxy-dimethyl-(2-methylprop-1-enyl)silane
• CAS: 149902-38-5
• 化学式: C₁₄H₂₆O₂Si
• 分子量: 254.445
• InChiKey: FTTGHBAULOPIAW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.19
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (E and Z)-2-(dimethyl-(2-methyl-1-propenyl)siloxy)-1-(methoxymethylidene)cyclohexane 在 2,6-二甲基吡啶 、 四丁基氟化铵 、 lithium perchlorate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 trans-2-hydroxy-1-(2-methyl-1-propenyl)cyclohexanecarboxaldehyde dimethyl acetal
  参考文献：
  名称：

  Intramolecular Anodic Olefin Coupling Reactions and the Use of Vinylsilanes

  摘要：

  Intramolecular anodic olefin coupling reactions involving vinylsilane groups have been studied. It was found that the previously successful predictive model for olefin coupling reactions based on an electrophilic attack of a radical cation onto an olefin did not successfully predict product formation for olefin coupling reactions involving vinylsilane terminating groups. Instead, these reactions were best described by viewing the initial addition of the radical cation to an olefin as if it occurred in a reversible ''radical-like'' fashion, in addition, reactions using a temporary silicon tether were shown to be compatible with the formation of quaternary carbons with control of relative stereochemistry. These reactions helped highlight the compatibility of the anodic olefin coupling reactions with extremely sensitive substrates. Finally, the results reported suggest that the mass balance of the intramolecular anodic olefin coupling reaction depends on the ease with which the initially formed cyclized product undergoes the second oxidation step.

  DOI：

  10.1021/ja00087a021
• 作为产物：
  描述：

  在 叔丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 21.0h， 生成 (E and Z)-2-(dimethyl-(2-methyl-1-propenyl)siloxy)-1-(methoxymethylidene)cyclohexane
  参考文献：
  名称：

  Intramolecular Anodic Olefin Coupling Reactions and the Use of Vinylsilanes

  摘要：

  Intramolecular anodic olefin coupling reactions involving vinylsilane groups have been studied. It was found that the previously successful predictive model for olefin coupling reactions based on an electrophilic attack of a radical cation onto an olefin did not successfully predict product formation for olefin coupling reactions involving vinylsilane terminating groups. Instead, these reactions were best described by viewing the initial addition of the radical cation to an olefin as if it occurred in a reversible ''radical-like'' fashion, in addition, reactions using a temporary silicon tether were shown to be compatible with the formation of quaternary carbons with control of relative stereochemistry. These reactions helped highlight the compatibility of the anodic olefin coupling reactions with extremely sensitive substrates. Finally, the results reported suggest that the mass balance of the intramolecular anodic olefin coupling reaction depends on the ease with which the initially formed cyclized product undergoes the second oxidation step.

  DOI：

  10.1021/ja00087a021

文献信息

• Intramolecular anodic olefin coupling reactions: the use of allyl- and vinylsilanes in the construction of quaternary carbons
  作者：Kevin D. Moeller、Christine M. Hudson、Luzviminda V. Tinao-Wooldridge

  DOI：10.1021/jo00065a003

  日期：1993.6

  Intramolecular anodic olefin coupling reactions involving the use of either an allylsilane as one of the olefin participants or a vinylsilane as part of a temporary silicon tether have been shown to be compatible with the formation of quaternary carbons.