(E)-[1-(4-chlorophenyl)-2-(triethoxysilyl)]ethene

• 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)-[1-(4-chlorophenyl)-2-(triethoxysilyl)]ethene
• 英文别名: (E)-1-(4-chlorophenyl)-2-(triethoxysilyl)ethene；(E)-(4-chlorostyryl)triethoxysilane；[(E)-2-(4-chlorophenyl)ethenyl]-triethoxysilane
• 化学式: C₁₄H₂₁ClO₃Si
• 分子量: 300.857
• InChiKey: OOOKUFLYHIQWIC-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.94
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N,N-二甲基甲酰胺 、 (E)-[1-(4-chlorophenyl)-2-(triethoxysilyl)]ethene 在 碘化铵 、 potassium fluoride 、 copper(II) nitrate trihydrate 、 氧气 作用下， 反应 25.0h， 以62%的产率得到(2E)-3-(4-chlorophenyl)acrylonitrile
  参考文献：
  名称：

  Copper-Mediated Transformation of Organosilanes to Nitriles with DMF and Ammonium Iodide

  摘要：

  Cyanation of aryl-, diaryldimethyl-, and styrylsilanes was developed for the first time under copper-mediated oxidative conditions using ammonium iodide and DMF as the combined source of nitrogen and carbon atom of the introduced cyano unit, respectively. The reaction was observed to proceed in a two-step process: initial conversion of organosilanes to their iodo intermediates and then cyanation. This method has a broad substrate scope with high functional group tolerance.

  DOI：

  10.1021/ol400659p
• 作为产物：
  描述：

  4-氯苯乙烯 、 三乙氧基硅烷 在 dirhodium tetraacetate 、 norbornene 、 1,3-双(二苯基膦)丙烷 、 三甲氧基磷 作用下， 以 甲苯 为溶剂， 以67%的产率得到(E)-[1-(4-chlorophenyl)-2-(triethoxysilyl)]ethene
  参考文献：
  名称：

  Dirhodium (II) 与邻位金属 DPPP 配合物在苯乙烯衍生物与烷氧基硅烷脱氢硅烷化中的独特催化性能

  摘要：

  在此，我们描述了用于邻位金属化 1,3-双（二苯基膦基）丙烷 (DPPP) 催化乙烯基芳烃与叔硅烷，特别是烷氧基硅烷脱氢硅烷化的二铑 (II) 配合物。这种催化方法显示出广泛的底物范围。在该协议中，乙烯基芳烃上的给电子和吸电子取代基都具有良好的耐受性。脱氢硅烷化反应与多种叔硅烷兼容，例如 (EtO) 3 SiH、(TMSO) 2 MeSiH、(HSiMe 2 ) 2 O、Et 3 SiH 和 Ph 3 SiH。机理研究表明，Rh 2 (OAc) 4的混合物、DPPP 和 P(OMe) 3提供了稳定且刚性的二铑 (II) 配合物，其中邻位金属化 DPPP 作为桥接配体，膦酸酯作为催化体系中的轴向配体。X 射线晶体衍射也支持了二铑 (II) 配合物的结构。进一步的实验证实，二铑（II）配合物可能是催化脱氢硅烷化反应的活性物质。对照实验表明，降冰片烯作为反应中的氢受体，在关键催化中间体铑硅物种的生成中起着至关重要的作用。

  DOI：

  10.1021/acscatal.1c02129

文献信息

• Efficient functionalization of olefins by arylsilanes catalyzed by palladium anionic complexes
  作者：E. Silarska、M. Majchrzak、B. Marciniec、A.M. Trzeciak

  DOI：10.1016/j.molcata.2016.07.023

  日期：2017.1

  organosilanes and different olefins was performed efficiently in the presence of anionic complexes, [CA]2[PdX4] and [CA]2[Pd2X6], where CA = imidazolium or pyridinium cation. The reaction proceeds according to a Pd(II)-mediated pathway, and Cu(OAc)2 acts as the re-oxidant of Pd(0) formed during the catalytic process. High product yields were obtained for differently substituted olefins at 80 °C in 4 h. Styrylsilanes

  有机硅烷和不同烯烃的偶联在阴离子络合物[CA] 2 [PdX 4 ]和[CA] 2 [Pd 2 X 6 ]的存在下有效进行，其中CA =咪唑鎓或吡啶鎓阳离子。反应根据Pd（II）介导的途径进行，Cu（OAc）2充当催化过程中形成的Pd（0）的再氧化剂。在80°C下4小时内，不同取代的烯烃获得了较高的产物收率。苯乙烯基硅烷在相同条件下反应，生成不对称的1,3-二烯。
• Well-defined NHC-rhodium hydroxide complexes as alkenehydrosilylation and dehydrogenative silylation catalysts
  作者：Byron J. Truscott、Alexandra M. Z. Slawin、Steven P. Nolan

  DOI：10.1039/c2dt31339a

  日期：——

  Alkene hydrosilylation and dehydrogenative silylation reactions, mediated by [Rh(cod)(NHC)(OH)] complexes (cod = 1,5-cyclooctadiene; NHC = N-heterocyclic carbene) are described. The study details a comparison of the catalytic activity and steric characteristics of four rhodium complexes bearing different NHC ligands. The novel [Rh(cod)(Ii-PrMe)(OH)] complex (Ii-PrMe = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidine) was designed to improve the reactivity of Rh(I)-hydroxides and proved to be a successful promoter of hydrosilylation and dehydrogenative silylation, displaying good stereo- and regiocontrol.

  烯烃氢硅烷化和脱氢硅烷化反应，通过[Rh(cod)(NHC)(OH)]配合物（cod = 1,5-环辛二烯；NHC = N-杂环卡宾）介导进行。研究详细比较了四种含不同NHC配体的铑配合物的催化活性和空间特性。新型[Rh(cod)(Ii-PrMe)(OH)]配合物（Ii-PrMe = 1,3-二异丙基-4,5-二甲基咪唑-2-亚基）旨在提高Rh(I)-氢氧化物的反应活性，并证明是氢硅烷化和脱氢硅烷化的有效促进剂，显示出良好的立体和区域控制性能。
• Cross-metathesis of vinylsilanes with olefins in the presence of Grubbs’ catalyst
  作者：Cezary Pietraszuk、Helmut Fischer、Małgorzata Kujawa、Bogdan Marciniec

  DOI：10.1016/s0040-4039(00)02201-2

  日期：2001.2

  Effective cross-metathesis of H2C-C(H)SIR3, where SiR3 = Si(OMe)(3), Si(OEt)(3), Si(OSiMe3)(3), with selected olefins in the presence of (PCy3),Cl2Ru(-CHPh) (I) is described. Treatment of p-substituted styrenes, l-alkenes and selected allyl derivatives H2C-CHCH2R' (R' = SiMe3, Si(OEt)(3), Ph, OPh) with an excess of H2C-C(H)SiR3 results in the formation of the respective cross-metathesis products with good yields and selectivities. The metallacarbene mechanism of the process is discussed. (C) 2001 Elsevier Science Ltd. All rights reserved.
• An efficient synthesis of functional stilbenes in Hiyama coupling reaction catalysed by H-spirophosphorane palladium complex
  作者：Anna Skarżyńska、Mariusz Majchrzak、Anna M. Trzeciak、Bogdan Marciniec

  DOI：10.1016/j.molcata.2011.09.025

  日期：2011.12

  An efficient Hiyama cross-coupling reaction of functionalised styrylsilanes with iodo- and bromobenzene has been performed using complex [PdCl2P(OCH2CMe2NH) OCH2CMe2NH2] as precatalyst. The styrylsilanes underwent cross-coupling reactions with excellent selectivity and yield, up to 99%, of the corresponding E-stilbenes. When (E)-[1-(4-bromophenyl)-2-(1,1,3,3,3-pentamethyldisiloxy)]ethene was used as a source of the silane, a homocoupling reaction took place and polymeric compound containing 0.77% of palladium in the form of Pd(0) nanoparticles was obtained. This material used as a catalyst made it possible to obtain 40% and 38% of the Hiyama cross-coupling product in two subsequent runs. (C) 2011 Elsevier B.V. All rights reserved.
• Distinct Catalytic Performance of Dirhodium(II) Complexes with <i>ortho</i>-Metalated DPPP in Dehydrosilylation of Styrene Derivatives with Alkoxysilanes
  作者：Wenkui Lu、Xiaoyu Zhu、Liqun Yang、Xiaoyu Wu、Xiaomin Xie、Zhaoguo Zhang

  DOI：10.1021/acscatal.1c02129

  日期：2021.8.20

  provided a stable and rigid dirhodium(II) complex with ortho-metalated DPPP as the bridging ligand and the phosphonate as the axial ligand in the catalytic system. The structure of the dirhodium(II) complexes was also supported by X-ray crystal diffraction. Further experiments confirmed that the dirhodium(II) complexes may be the active species that catalyze the dehydrosilylation reaction. Control experiments

  在此，我们描述了用于邻位金属化 1,3-双（二苯基膦基）丙烷 (DPPP) 催化乙烯基芳烃与叔硅烷，特别是烷氧基硅烷脱氢硅烷化的二铑 (II) 配合物。这种催化方法显示出广泛的底物范围。在该协议中，乙烯基芳烃上的给电子和吸电子取代基都具有良好的耐受性。脱氢硅烷化反应与多种叔硅烷兼容，例如 (EtO) 3 SiH、(TMSO) 2 MeSiH、(HSiMe 2 ) 2 O、Et 3 SiH 和 Ph 3 SiH。机理研究表明，Rh 2 (OAc) 4的混合物、DPPP 和 P(OMe) 3提供了稳定且刚性的二铑 (II) 配合物，其中邻位金属化 DPPP 作为桥接配体，膦酸酯作为催化体系中的轴向配体。X 射线晶体衍射也支持了二铑 (II) 配合物的结构。进一步的实验证实，二铑（II）配合物可能是催化脱氢硅烷化反应的活性物质。对照实验表明，降冰片烯作为反应中的氢受体，在关键催化中间体铑硅物种的生成中起着至关重要的作用。