ethyldimethyl[(1-phenylethenyl)oxy]silane

• 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: ethyldimethyl[(1-phenylethenyl)oxy]silane
• 英文别名: ethyldimethyl[(1-phenylvinyl)oxy]silane；Ethyl-dimethyl-(1-phenylethenoxy)silane
• 化学式: C₁₂H₁₈OSi
• 分子量: 206.36
• InChiKey: QJHJYSVFDFIQRR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  Dimethyl-(1-phenyl-ethoxy)-vinyl-silane 在 [(C5Me5)Rh(vinyltrimethylsilane)2] 作用下， 反应 48.0h， 生成 ethyldimethyl[(1-phenylethenyl)oxy]silane
  参考文献：
  名称：

  [C5Me5Rh(烯烃)2]配合物催化的氢/氘交换反应和转移氢化反应：烷氧基硅烷转化为甲硅烷基烯醇盐†

  摘要：

  已经制备了一系列 [C5Me5Rh(CH2CHR)2] 配合物 (1a-e)，其中烯烃带有庞大的甲硅烷基取代基，R = (a) SiMe3，(b) SiMe2OEt，(c) Si(OiPr)3， (d) SiMe(OSiMe3)2，(e) SiPh2OiPr。1c 的固态结构已通过 X 射线晶体学确定。当配合物 1a 在氘代溶剂（C6D6、C6D5CD3、C6D5Cl 或 (CD3)2CO）中加热 (50 °C) 时，氘会被结合到烯烃位点中。在较高温度下的热解导致 SiMe3 和 C5Me5 基团的进一步 H/D 交换和氘化。用添加的底物（苯胺、MeOtBu、MeOSiMe3、Cp2Fe、环戊烯或 EtOAc）在 C6D6 中加热 1a，通过氘从 C6D6 穿梭到烯烃位点，然后进入底物的某些位点，导致这些底物的氘化。1a 在乙烯基三甲基硅烷存在下在较高温度下的热解导致 C-Si 键断裂并生成硅杂环戊二烯配合物

  DOI：

  10.1021/ja984409o

文献信息

• Analysis of the enantioselectivities and initial rates of the hydrosilylation of acetophenone catalyzed by [Rh(cod)Cl]2/(chiral diphosphine). The quantitative analysis of ligand effects
  作者：Clementina Reyes、Alfred Prock、Warren P. Giering

  DOI：10.1016/s0022-328x(02)02221-0

  日期：2003.4

  Through the application of the quantitative analysis of ligand effects (QALE) method to the study of the hydrosilylation of acetophenone, we have shown, for the first time, that the initial rate and enantioselectivity of a complicated catalytic system responds in a rational manner to the variations in the stereoelectronic properties of the silane. The reactions (in benzene-d6 at 63 °C) were catalyzed

  通过将配体效应定量分析（QALE）方法用于对苯乙酮的氢化硅烷化研究，我们首次表明，复杂催化体系的初始速率和对映选择性以合理的方式响应于苯乙酮。硅烷的立体电子性质的变化。该反应（在63°C的苯-d 6中）通过[Rh（cod）Cl] 2 /（手性二膦）（手性二膦=（R）-BINAP [（R）-（+）-2.2'-双（二苯基膦基）-1,1'-联萘基]，（R，R）-甲苯基-BINAP [（R）-（+）-2,2'-双（二-对甲苯基膦基）-1,1'-联萘基]，（R，R）-Me-DUPHOS [（R，R）-（-）-1,2-Bis-2,5-二甲基膦酰基苯），（R，R）-DIOP [（R，R）-（-） -2,3- ø -isopropylidine -2,3-二羟基-1,4-双（二苯基膦基）丁烷]，和（- [R）-QUINAP [（[R ）- （+） - 1-（2-二苯基膦基-1-萘基）。氢化硅烷化产物（CH
• Cobalt-Catalyzed Hydrosilation/Hydrogen-Transfer Cascade Reaction: A New Route to Silyl Enol Ethers
  作者：Thomas W. Lyons、Maurice Brookhart

  DOI：10.1002/chem.201301502

  日期：2013.7.29

  Capitalizing on cobalt: A new route to silyl enol ethers employing a Co‐catalyzed cascade reaction featuring a tandem hydrosilation/hydrogen‐transfer reaction is reported. The low catalyst loading, mild reaction conditions, and unique η2‐silane resting state showcase the impressive utility of this seldom used transition‐metal catalyst in CH activation reactions (see scheme; VTMS = vinyltrimethylsilane;

  利用钴：报道了一种采用共催化级联反应的串联硅烷化/氢转移反应的甲硅烷基烯醇醚的新途径。低催化剂负载，温和的反应条件，以及独特的η 2 -硅烷静止状态展示在C此很少使用过渡金属催化剂的令人印象深刻的效用 ħ活化反应（参见方案; VTMS =乙烯基三甲基硅烷;的Cp * = 1,2， 3,4,5-戊甲基环戊二烯）。
• Base-Free Dehydrogenative Coupling of Enolizable Carbonyl Compounds with Silanes
  作者：C. David F. Königs、Hendrik F. T. Klare、Yasuhiro Ohki、Kazuyuki Tatsumi、Martin Oestreich

  DOI：10.1021/ol301089r

  日期：2012.6.1

  A dehydrogenative coupling between enolizable carbonyl compounds and equimolar amounts of triorganosilanes catalyzed by a tethered ruthenium complex with a Ru-S bond is reported. The complex Is assumed to fulfill a dual role by activating the Si-H bond to release a silicon electrophile and by abstracting an a-proton from the intermediate silylcarboxonium ion, only liberating dihydrogen as the sole byproduct. Reaction rates are exceedingly high at room temperature with very low loadings of the ruthenium catalyst.
• An Air-Stable Dimeric Ru–S Complex with an NHC as Ancillary Ligand for Cooperative Si–H Bond Activation
  作者：Susanne Bähr、Antoine Simonneau、Elisabeth Irran、Martin Oestreich

  DOI：10.1021/acs.organomet.6b00110

  日期：2016.4.11

  The preparation of a coordinatively unsaturated NHC ruthenium complex with a tethered 2,6-dimesitylphenyl thiolate is described. Unlike related mononudear phosphine complexes, the NHC complex forms an air-stable dimer with bridging sulfur ligands in both the solid state and solution. The dinuclear complex is a precatalyst and activates Si H bonds upon heat-or donor-assisted dissociation into the catalytically active monomer. Its usefulness is illustrated with representative dehydrogenative Si X coupling and hydrosilylation reactions.