chlorotris(4-isopropylphenyl)silane | 1373216-32-0

• 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: chlorotris(4-isopropylphenyl)silane
• 英文别名: tris(4-isopropylphenyl)silyl chloride；Chloro-tris(4-propan-2-ylphenyl)silane
• CAS: 1373216-32-0
• 化学式: C₂₇H₃₃ClSi
• 分子量: 421.098
• InChiKey: VRKCTBFYOXHJBJ-UHFFFAOYSA-N

物化性质

• 沸点：
  468.9±45.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.26
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  chlorotris(4-isopropylphenyl)silane 在 lithium amide 作用下， 以 四氢呋喃 为溶剂， 以80%的产率得到(4-iPrC6H4)3SiNH2
  参考文献：
  名称：

  Expanding the Steric Coverage Offered by Bis(amidosilyl) Chelates: Isolation of Low-Coordinate N-Heterocyclic Germylene Complexes

  摘要：

  The synthesis and coordination chemistry of a series of dianionic bis(amido)silyl and bis(amido)disilyl, [NSiN] and [NSi-SiN], chelates with N-bound aryl or sterically modified triarylsilyl (SiAr3) groups is reported. In order to provide a consistent comparison of the steric coverage afforded by each ligand construct, various two-coordinate N-heterocyclic germylene complexes featuring each ligand set were prepared and oxidative S-atom transfer chemistry was explored. In the cases where clean oxidation transpired, sulfido-bridged centrosymmetric germanium(IV) dimers of the general form [LGe(mu-S)](2) (L = bis(amidosilyl) ligands) were obtained in lieu of the target monomeric germanethiones with discrete Ge=S double bonds. These results indicate that the reported chelates possess sufficient conformational flexibility to allow for the dimerization of LGe=S units to occur. Notably, the new triarylsilyl groups (4-RC6H4)(3)Si- (R = Bu-t and Pr-i) still offer considerably expanded degrees of steric coverage relative to the parent congener, -SiPh3, and thus the use of substituted triarylsilyl groups within ligand design strategies should be a generally useful concept in advancing low-coordination main group and transition-metal chemistry.

  DOI：

  10.1021/ic300495k
• 作为产物：
  描述：

  tris(4-isopropylphenyl)silane 在 磺酰氯 作用下， 以 四氯化碳 为溶剂， 反应 4.0h， 以78%的产率得到chlorotris(4-isopropylphenyl)silane
  参考文献：
  名称：

  基于甲硅烷基化的动力学拆分的线性自由能关系和速率研究：机理见解

  摘要：

  探索了不同的对位取代的三苯基甲硅烷基氯的取代基对基于甲硅烷基化的动力学拆分的影响。给电子基团减慢反应速率并提高选择性，而吸电子基团增加反应速率并降低选择性。发现线性自由能关系都选择性因素和初始利率为σ相关对哈米特参数。当仅使用烷基取代基时，还观察到选择性因子与Charton值之间的相关性较弱，但是当引入具有更多电子效应的取代基时，则不存在选择性因子与Charton值的弱相关性。速率数据表明，在过渡状态下会发生明显的电荷重新分布，而正电荷会总体上减少。Hammond假设可以最好地理解源自选择性因子的线性自由能关系。早期和晚期过渡态描述了底物在过渡态中的参与量，因此描述了两种对映异构体的非对映体过渡态之间的能量差。这项工作突出了我们在基于甲硅烷基化的动力学拆分中努力理解选择性的机理和起源的努力。

  DOI：

  10.1021/jo402569h

文献信息

• Diastereoselective and Enantioselective Silylation of 2-Arylcyclohexanols
  作者：Li Wang、Ravish K. Akhani、Sheryl L. Wiskur

  DOI：10.1021/acs.orglett.5b00919

  日期：2015.5.15

  The silylation-based kinetic resolution of trans 2-arylcyclohexanols was accomplished by employing a triaryl silyl chloride as the derivatizing reagent with a commercially available isothiourea catalyst. The methodology is selective for the trans diastereomer over the cis, which provides an opportunity to selectively derivatize one stereoisomer out of a mixture of four. By employing this technology, a facile, convenient method to form a highly enantiomerically enriched silylated alcohol was accomplished through a one-pot reduction-silylation sequence that started with a 2-aryl-substituted ketone.