{[4-(3-Methoxyphenyl)but-1-yn-1-yl]oxy}tri(propan-2-yl)silane | 765906-58-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: {[4-(3-Methoxyphenyl)but-1-yn-1-yl]oxy}tri(propan-2-yl)silane
• 英文别名: 4-(3-methoxyphenyl)but-1-ynoxy-tri(propan-2-yl)silane
• CAS: 765906-58-9
• 化学式: C₂₀H₃₂O₂Si
• 分子量: 332.558
• InChiKey: URBSZWIBAYKQDE-UHFFFAOYSA-N

物化性质

• 沸点：
  392.6±44.0 °C(Predicted)
• 密度：
  0.938±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.78
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  {[4-(3-Methoxyphenyl)but-1-yn-1-yl]oxy}tri(propan-2-yl)silane 在 双三氟甲烷磺酰亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 Triisopropyl-(6-methoxy-3,4-dihydro-naphthalen-1-yloxy)-silane 、 Triisopropyl-(8-methoxy-3,4-dihydro-naphthalen-1-yloxy)-silane
  参考文献：
  名称：

  Brønsted Acid-Promoted Cyclizations of Siloxyalkynes with Arenes and Alkenes

  摘要：

  We have described the first Brønsted acid-mediated cyclizations of siloxyalkynes with simple arenes and alkenes to afford substituted tetralone and cyclohexenone derivatives. The most notable aspect of the carbocyclizations involving siloxyalkynes is the ability to employ a range of substrates that are not restricted to those containing electron-rich arenes and alkenes. The key mechanistic feature of the reaction is the generation of a highly reactive ketenium ion upon protonation of siloxyalkyne. We believe that the low nucleophilicty of the counteranion is crucial for enabling the formation and effective interception of this highly reactive intermediate.

  DOI：

  10.1021/ja046586x
• 作为产物：
  描述：

  3-甲氧基溴苄 在 sodium hydroxide 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 6.0h， 生成 {[4-(3-Methoxyphenyl)but-1-yn-1-yl]oxy}tri(propan-2-yl)silane
  参考文献：
  名称：

  Brønsted Acid-Promoted Cyclizations of Siloxyalkynes with Arenes and Alkenes

  摘要：

  We have described the first Brønsted acid-mediated cyclizations of siloxyalkynes with simple arenes and alkenes to afford substituted tetralone and cyclohexenone derivatives. The most notable aspect of the carbocyclizations involving siloxyalkynes is the ability to employ a range of substrates that are not restricted to those containing electron-rich arenes and alkenes. The key mechanistic feature of the reaction is the generation of a highly reactive ketenium ion upon protonation of siloxyalkyne. We believe that the low nucleophilicty of the counteranion is crucial for enabling the formation and effective interception of this highly reactive intermediate.

  DOI：

  10.1021/ja046586x

文献信息

• Brønsted acid-promoted cyclizations of siloxy alkynes with unactivated arenes, alkenes, and alkynes
  作者：Liming Zhang、Jianwei Sun、Sergey A. Kozmin

  DOI：10.1016/j.tet.2006.06.037

  日期：2006.12

  found that trifluoromethane sulfonimide (HNTf2) proved to be a superior promoter of these reactions compared to a range of other Brønsted acids. This finding could be attributed to a high acidity of HNTf2 in aprotic organic solvents combined with a low nucleophilicity of the NTf2− anion. Depending on the nature of the nucleophile, the carbocyclizations proceeded either via 6-endo-dig or 5-endo-dig manifolds

  在本文中，我们描述了开发新的碳-碳键形成过程的一般概念，该概念基于布朗斯台德酸介导的甲硅烷氧基炔烃的活化作用，然后有效截获所得的高反应性离子通过未活化的芳烃，烯烃或炔烃。我们发现，与一系列其他布朗斯台德酸相比，三氟甲烷磺酰亚胺（HNTf 2）被证明是这些反应的优良促进剂。这一发现可以归因于HNTf的高酸度2与所述NTF的低亲核性组合非质子有机溶剂2 -阴离子。根据亲核试剂的性质，碳环化可通过6-endo-dig或5个内挖式歧管。在1-甲硅烷基-1,5-二炔的情况下，环化反应伴随着卤化物的抽象或芳基化。