(R)-triethyl(1-phenylethoxy)silane | 577749-62-3

• 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: (R)-triethyl(1-phenylethoxy)silane
• CAS: 577749-62-3
• 化学式: C₁₄H₂₄OSi
• 分子量: 236.429
• InChiKey: ZPRKOXNXVHWYMB-CYBMUJFWSA-N

物化性质

• 沸点：
  273.3±9.0 °C(Predicted)
• 密度：
  0.895±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  16.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  (S)-triethyl(1-phenylethoxy)silane 在 三乙基硅烷 、 [(POCOP)Ir(H)(acetone)]+[B(C6F5)4]- 作用下， 以 氯苯 为溶剂， 反应 24.0h， 生成 (R)-triethyl(1-phenylethoxy)silane
  参考文献：
  名称：

  布鲁克哈特阳离子铱(III)钳形配合物催化羰基氢化硅烷化机理的深入研究

  摘要：

  新的实验结果表明，对目前公认的由 Brookhart 引入的铱 (III) 钳形复合物催化的羰基氢化硅烷化机制进行了部分修订。使用硅立体硅烷作为立体化学探针会导致外消旋化而不是硅原子构型的反转。然而，外消旋化的程度受硅烷/羰基化合物比例的影响，并且在硅烷过量时观察到反转。独立制备甲硅烷基羰基鎓离子中间体并测试其反应性有助于使这种效果合理化。立体化学分析连同这些对照实验、严格的多核 NMR 分析和量子化学计算清楚地证明另一个硅烷分子参与了氢化物转移。

  DOI：

  10.1021/ja503254f

文献信息

• Synthesis and Lewis acid properties of a ferrocene-based planar-chiral borenium cation
  作者：Jiawei Chen、Roger A. Lalancette、Frieder Jäkle

  DOI：10.1039/c3cc41556b

  日期：——

  The first planar chiral ferrocenylborenium species (pR)-3+ is obtained in the enantiopure form by halide abstraction from the corresponding chloroborane adduct (pR)-2 using Krossing's salt. Competition experiments suggest that the Lewis acidity of (pR)-3+ is higher than that of B(C6F5)3 towards anions and slightly lower towards neutral Lewis bases. The ferrocenylborenium species (pR)-3+ is examined as a catalyst for the stereoselective hydrosilylation of ketones.

  第一种平面手性铁酰基硼阳离子（pR）-3+是通过使用Krossing的盐从相应的氯硼烷加合物（pR）-2中抽取卤素而以对映体纯净的形式获得的。竞争实验表明，（pR）-3+的路易斯酸性对阴离子的强度高于B(C6F5)3，而对中性路易斯碱的强度则稍低。铁酰基硼阳离子（pR）-3+作为催化剂被研究用于酮的立体选择性氢硅化反应。
• Cationic Carboxylato Complexes of Dirhodium(II) with Oxo Thioethers: Catalysts for Silane Alcoholysis under Homogeneous and Liquid-Liquid Biphasic Conditions
  作者：Andrea Biffis、Marino Basato、Marianna Brichese、Luca Ronconi、Cristina Tubaro、Alessandra Zanella、Claudia Graiff、Antonio Tiripicchio

  DOI：10.1002/adsc.200700167

  日期：2007.11.5

  A set of cationic dirhodium(II) complexes with oxo thioethers was prepared and employed as catalysts for the silane alcoholysis reaction. The complexes were found to be highly active under homogeneous conditions, both in the absence and in the presence of a solvent, including coordinating solvents such as N,N-dimethylformamide; the catalysts could be conveniently employed in concentrations as low as

  制备了一组与羰基硫醚的阳离子二吡啶（II）配合物，并将其用作硅烷醇解反应的催化剂。发现该络合物在均相条件下，在不存在和存在溶剂（包括配位溶剂，例如N，N）的情况下均具有高活性-二甲基甲酰胺；该催化剂可方便地以低至0.01 mol％的浓度使用，并且在24小时后记录的最大TON为30000。在液-液两相条件下也使用相同的催化剂，并以离子液体作为含催化剂的相：在这些条件下观察到相当的催化活性，并且含催化剂的相可以回收和再循环。在这项工作的框架内，还制备了一种手性阳离子（II）络合物。不幸的是，尝试用该催化剂进行外消旋醇的动力学拆分。
• Hidden Enantioselective Hydrogenation of N-Silyl Enamines and Silyl Enol Ethers in Net C═N and C═O Hydrosilylations Catalyzed by Ru–S Complexes with One Monodentate Chiral Phosphine Ligand
  作者：Susanne Bähr、Martin Oestreich

  DOI：10.1021/acs.organomet.7b00030

  日期：2017.2.27

  Ruthenium thiolate complexes with one chiral monodentate phosphine ligand are applied to enantioselective hydrosilylation of enolizable 'mines and ketones. The structural features of the catalyst exclude the presence of more than one phosphine ligand at the ruthenium center in the enantioselectivity-determining step. The enantiomeric excesses obtained in these reduction reactions ate moderate (up to 66% ee), but the stereochemical outcome enables an experimental analysis of the reaction pathways operative in this catalysis. A two-step sequence consisting of successive N-Si/O Si dehydrogenative coupling and enamine/enol ether hydrogenation is, the prevailing mechanisin Of action. Both steps involve cooperative bond activation at the Ru-S bond of the coordinatively unsaturated ruthenium complex: Si-H bond activation in the dehydrogenative coupling and heterolytic H-H splitting in the hydrogenation. Previously documented side reactions such as deprotonation/protonation equilibria as well as competing direct C=N or C=O hydrogenation have been excluded.