methyl (E)-3-[[2,2-dimethyl-4-(trimethylsilylmethyl)cyclohex-3-en-1-yl]methoxy]prop-2-enoate | 245670-15-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl (E)-3-[[2,2-dimethyl-4-(trimethylsilylmethyl)cyclohex-3-en-1-yl]methoxy]prop-2-enoate
• CAS: 245670-15-9
• 化学式: C₁₇H₃₀O₃Si
• 分子量: 310.509
• InChiKey: KHONOLBBVKIBOT-MDZDMXLPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.39
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (E)-3-[[2,2-dimethyl-4-(trimethylsilylmethyl)cyclohex-3-en-1-yl]methoxy]prop-2-enoate 在 二氯二甲基硅烷 、 对甲苯亚磺酸 作用下， 以 萘烷 、 二氯甲烷 、 水 为溶剂， 反应 99.0h， 生成 methyl 2-(6,6-dimethyl-8-methylidene-3-oxabicyclo[3.3.1]nonan-2-yl)acetate 、 methyl 2-(9,9-dimethyl-8-methylidene-3-oxabicyclo[3.3.1]nonan-2-yl)acetate
  参考文献：
  名称：

  Silicon-Controlled Intramolecular Thermal H-Ene Reaction – A New Access to a Key Intermediate of (±)-cis-γ-Irone

  摘要：

  The primordial influence of the silyl group in an intramolecular thermal H-ene reaction is reported. The silyl group lowered the energy of the transition state and allowed the reaction to proceed at a lower temperature than that of the simple all-carbon analog, thereby excluding the formation of undesirable by-products. This sequence has been applied for new access to a key intermediate in the diastereoselective synthesis of (+/-)-cis-gamma-irone with high chemocontrol and significantly improved overall yield.

  DOI：

  10.1002/(sici)1099-0690(199908)1999:8<1825::aid-ejoc1825>3.0.co;2-5
• 作为产物：
  描述：

  Ethyl 4-diethoxyphosphoryloxy-2,2-dimethylcyclohex-3-ene-1-carboxylate 在 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) N-甲基吗啉 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 84.5h， 生成 methyl (E)-3-[[2,2-dimethyl-4-(trimethylsilylmethyl)cyclohex-3-en-1-yl]methoxy]prop-2-enoate
  参考文献：
  名称：

  Silicon-Controlled Intramolecular Thermal H-Ene Reaction – A New Access to a Key Intermediate of (±)-cis-γ-Irone

  摘要：

  The primordial influence of the silyl group in an intramolecular thermal H-ene reaction is reported. The silyl group lowered the energy of the transition state and allowed the reaction to proceed at a lower temperature than that of the simple all-carbon analog, thereby excluding the formation of undesirable by-products. This sequence has been applied for new access to a key intermediate in the diastereoselective synthesis of (+/-)-cis-gamma-irone with high chemocontrol and significantly improved overall yield.

  DOI：

  10.1002/(sici)1099-0690(199908)1999:8<1825::aid-ejoc1825>3.0.co;2-5

文献信息

• Silicon-Controlled Intramolecular Thermal H-Ene Reaction – A New Access to a Key Intermediate of (±)-cis-γ-Irone
  作者：Honoré Monti、Gilles Laval、Michel Féraud

  DOI：10.1002/(sici)1099-0690(199908)1999:8<1825::aid-ejoc1825>3.0.co;2-5

  日期：1999.8

  The primordial influence of the silyl group in an intramolecular thermal H-ene reaction is reported. The silyl group lowered the energy of the transition state and allowed the reaction to proceed at a lower temperature than that of the simple all-carbon analog, thereby excluding the formation of undesirable by-products. This sequence has been applied for new access to a key intermediate in the diastereoselective synthesis of (+/-)-cis-gamma-irone with high chemocontrol and significantly improved overall yield.