(E)-5-(trimethylsilanyl)-2-phenyldec-3-ene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-5-(trimethylsilanyl)-2-phenyldec-3-ene
• 英文别名: trimethyl-[(E)-2-phenyldec-3-en-5-yl]silane
• 化学式: C₁₉H₃₂Si
• 分子量: 288.549
• InChiKey: AEDUAHIONTZXQW-FOCLMDBBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.64
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  四苯硼钠 、 在 三苯基膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 四氢呋喃 为溶剂， 反应 3.25h， 以53%的产率得到(E)-5-(trimethylsilanyl)-2-phenyldec-3-ene
  参考文献：
  名称：

  Regioselective Catalytic Transformations Involving β-Silyl-Substituted (η³-Allyl)palladium Complexes:  An Efficient Route to Functionalized Allylsilanes

  摘要：

  Various alkyl derivatives of 1-(trimethylsilanyl)but-3-en-2-ol acetate (1a-e) undergo regioselective palladium-catalyzed nucleophilic substitution via beta-silyl-substituted (eta(3)-allyl)palladium intermediates. With external nucleophiles, such as malonates and enolates, the nucleophilic substitution occurs with complete allylic rearrangement, providing functionalized allylsilanes as building blocks of high synthetic potential. Internal nucleophiles, such as disilanes and NaBPh4, afford bisallylic disilanes and (allylsilyl)benzene derivatives with good regioselectivity. For both types of nucleophiles, the double bond geometry of the resulting allylsilane is selectively traits. The beta-silyl-substituted (eta(3)-allyl)palladium intermediates of the reaction were also isolated. The H-1 NMR studies indicate selective formation of the syn-isomer of the key (eta(3)-allyl)palladium intermediates, which explains the high trans-selectivity of the double bond formation in the allylsilane products. According to the C-13 NMR studies, the beta-silyl functionality exerts deshielding effects on the nearest allylic terminal carbon (C3), which can be ascribed to hyperconjugative interactions between the silyl functionality and the allylpalladium moiety. It was concluded that, together with the steric effects of the silyl group, these electronic interactions are responsible for the high regioselectivity of the nucleophilic attack in the catalytic process.

  DOI：

  10.1021/jo991172l

文献信息

• Regioselective Catalytic Transformations Involving β-Silyl-Substituted (η³-Allyl)palladium Complexes:  An Efficient Route to Functionalized Allylsilanes
  作者：István Macsári、Eike Hupe、Kálmán J. Szabó

  DOI：10.1021/jo991172l

  日期：1999.12.1

  Various alkyl derivatives of 1-(trimethylsilanyl)but-3-en-2-ol acetate (1a-e) undergo regioselective palladium-catalyzed nucleophilic substitution via beta-silyl-substituted (eta(3)-allyl)palladium intermediates. With external nucleophiles, such as malonates and enolates, the nucleophilic substitution occurs with complete allylic rearrangement, providing functionalized allylsilanes as building blocks of high synthetic potential. Internal nucleophiles, such as disilanes and NaBPh4, afford bisallylic disilanes and (allylsilyl)benzene derivatives with good regioselectivity. For both types of nucleophiles, the double bond geometry of the resulting allylsilane is selectively traits. The beta-silyl-substituted (eta(3)-allyl)palladium intermediates of the reaction were also isolated. The H-1 NMR studies indicate selective formation of the syn-isomer of the key (eta(3)-allyl)palladium intermediates, which explains the high trans-selectivity of the double bond formation in the allylsilane products. According to the C-13 NMR studies, the beta-silyl functionality exerts deshielding effects on the nearest allylic terminal carbon (C3), which can be ascribed to hyperconjugative interactions between the silyl functionality and the allylpalladium moiety. It was concluded that, together with the steric effects of the silyl group, these electronic interactions are responsible for the high regioselectivity of the nucleophilic attack in the catalytic process.