(Z)-1-Iodo-3-(methoxymethoxy)-5-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1-pentene | 158074-73-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (Z)-1-Iodo-3-(methoxymethoxy)-5-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1-pentene
• 英文别名: tert-butyl-[(Z)-5-iodo-3-(methoxymethoxy)pent-4-enoxy]-dimethylsilane
• CAS: 158074-73-8
• 化学式: C₁₃H₂₇IO₃Si
• 分子量: 386.346
• InChiKey: SXIKPCILWBXOOH-CLFYSBASSA-N

物化性质

• 沸点：
  336.2±42.0 °C(predicted)
• 密度：
  1.242±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.34
• 重原子数：
  18
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (Z)-1-Iodo-3-(methoxymethoxy)-5-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1-pentene 在 草酰氯 、 四丁基氟化铵 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 4.08h， 生成 (3α,3aα,6β,7aα)-2,3,4,6,7,7a-Hexahydro-6-(methoxymethoxy)-1-methyl-3-(dimethylphenylsilyl)-3a-<3,4-(methylenedioxy)phenyl>indole
  参考文献：
  名称：

  Approach to 6a-Epipretazettine and 6a-Epiprecriwelline via an Intramolecular 2-Azaallyl Anion Cycloaddition Reaction

  摘要：

  An intramolecular 2-azaallyl anion cycloaddition with a diene produced the 2,3,4,6,7,7a-hexahydroindol 33 with complete control of relative stereochemistry, thus providing the first example of the e use of such a cycloaddition in an approach to a relatively complex target molecule. The 2-azaallyl anion was generated by tin-lithium exchange of the (2-azaallyl)stannane 32. The stannane was prepared by a convergent route using a Stille coupling of the vinyl bromide 14 with the vinylstannane 28, providing the diene 29. An unexpected isomerization occurred in the Stille coupling. Transformation of the cycloadduct 33 to the allylic methyl ethers 36 and 37 produced potential precursors of 6a-epiprecriwelline (4) and 6a-epipretazettine (3), respectively. The inability to carry out an oxidative desilylation thwarted the completion of the syntheses of these alkaloids.

  DOI：

  10.1021/jo00098a026
• 作为产物：
  描述：

  3-(叔丁基-二甲基-硅烷基OXY)-丙醛 在 正丁基锂 、 四甲基乙二胺 、 碘 、 potassium diazodicarboxylate 、 溶剂黄146 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 38.92h， 生成 (Z)-1-Iodo-3-(methoxymethoxy)-5-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1-pentene
  参考文献：
  名称：

  Approach to 6a-Epipretazettine and 6a-Epiprecriwelline via an Intramolecular 2-Azaallyl Anion Cycloaddition Reaction

  摘要：

  An intramolecular 2-azaallyl anion cycloaddition with a diene produced the 2,3,4,6,7,7a-hexahydroindol 33 with complete control of relative stereochemistry, thus providing the first example of the e use of such a cycloaddition in an approach to a relatively complex target molecule. The 2-azaallyl anion was generated by tin-lithium exchange of the (2-azaallyl)stannane 32. The stannane was prepared by a convergent route using a Stille coupling of the vinyl bromide 14 with the vinylstannane 28, providing the diene 29. An unexpected isomerization occurred in the Stille coupling. Transformation of the cycloadduct 33 to the allylic methyl ethers 36 and 37 produced potential precursors of 6a-epiprecriwelline (4) and 6a-epipretazettine (3), respectively. The inability to carry out an oxidative desilylation thwarted the completion of the syntheses of these alkaloids.

  DOI：

  10.1021/jo00098a026