(E)-tert-butyl-(3-methyl-6-(trimethylsilanyl)hex-3-en-5-ynyloxy)diphenylsilane | 498556-45-9

• 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: (E)-tert-butyl-(3-methyl-6-(trimethylsilanyl)hex-3-en-5-ynyloxy)diphenylsilane
• CAS: 498556-45-9
• 化学式: C₂₆H₃₆OSi₂
• 分子量: 420.742
• InChiKey: VKDRMAFHNOAAFH-HZHRSRAPSA-N

物化性质

• 沸点：
  460.2±38.0 °C(Predicted)
• 密度：
  0.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.78
• 重原子数：
  29.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (E)-tert-butyl-(3-methyl-6-(trimethylsilanyl)hex-3-en-5-ynyloxy)diphenylsilane 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 12.0h， 以100%的产率得到(E)-tert-butyl-(3-methylhex-3-en-5-ynyloxy)diphenylsilane
  参考文献：
  名称：

  Dimethylzinc-Mediated Additions of Alkenylzirconocenes to Aldimines. New Methodologies for Allylic Amine and C-Cyclopropylalkylamine Syntheses

  摘要：

  Hydrozirconation of alkynes with zirconocene hydrochloride followed by in situ transmetalation to dimethylzinc provides access to reactive alkenyl organometallic reagents from readily available precursors. Upon addition of imines, 1,2-attack leads to synthetically useful allylic amine building blocks. In the presence of CH2I2 or CH2Cl2, the N-metalated allylic amide intermediate is cyclopropanated and C-cyclopropylalkylamines are formed in high yield and excellent diastereoselectivities favoring the anti products. The use of enynes as starting materials for this domino reaction provides conjugated biscyclopropanes and thus allows the stereoselective formation of five new carbon-carbon bonds. A transition state that explains the need for both zirconocene complex and alkyl zinc in the cyclopropanation reaction is proposed.

  DOI：

  10.1021/ja028092a
• 作为产物：
  描述：

  (E)-4-iodo-3-methylbut-3-en-1-ol 在 咪唑 、 4-二甲氨基吡啶 、 copper(l) iodide 、 四(三苯基膦)钯 、 二异丙胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.17h， 生成 (E)-tert-butyl-(3-methyl-6-(trimethylsilanyl)hex-3-en-5-ynyloxy)diphenylsilane
  参考文献：
  名称：

  Dimethylzinc-Mediated Additions of Alkenylzirconocenes to Aldimines. New Methodologies for Allylic Amine and C-Cyclopropylalkylamine Syntheses

  摘要：

  Hydrozirconation of alkynes with zirconocene hydrochloride followed by in situ transmetalation to dimethylzinc provides access to reactive alkenyl organometallic reagents from readily available precursors. Upon addition of imines, 1,2-attack leads to synthetically useful allylic amine building blocks. In the presence of CH2I2 or CH2Cl2, the N-metalated allylic amide intermediate is cyclopropanated and C-cyclopropylalkylamines are formed in high yield and excellent diastereoselectivities favoring the anti products. The use of enynes as starting materials for this domino reaction provides conjugated biscyclopropanes and thus allows the stereoselective formation of five new carbon-carbon bonds. A transition state that explains the need for both zirconocene complex and alkyl zinc in the cyclopropanation reaction is proposed.

  DOI：

  10.1021/ja028092a