(E)-triethoxy(4-methoxystyryl)silane | 105281-61-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (E)-triethoxy(4-methoxystyryl)silane
• 英文别名: triethoxy-[(E)-2-(4-methoxyphenyl)ethenyl]silane
• CAS: 105281-61-6
• 化学式: C₁₅H₂₄O₄Si
• 分子量: 296.439
• InChiKey: FVHHTKIHDFWQCE-OUKQBFOZSA-N

物化性质

• 沸点：
  350.1±25.0 °C(Predicted)
• 密度：
  1.015±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-triethoxy(4-methoxystyryl)silane 、 N,N-二甲基甲酰胺 在 碘化铵 、 potassium fluoride 、 copper(II) nitrate trihydrate 、 氧气 作用下， 反应 25.0h， 以64%的产率得到
  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：

  三乙氧基硅烷 、 4-乙炔基苯甲醚 在 platinum(II) chloride 2-dicyclohexyl-phosphino-2',4',6'-triisopropylbiphenyl 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以65%的产率得到(E)-triethoxy(4-methoxystyryl)silane
  参考文献：
  名称：

  Xphos ligand and platinum catalysts: A versatile catalyst for the synthesis of functionalized β-(E)-vinylsilanes from terminal alkynes

  摘要：

  Hydrosilylation of functionalized terminal arylalkynes with a variety of silanes catalyzed by PtCl(2) or PtO(2) in the presence of the air-stable and bulky Xphos ligand was investigated. Regardless of the electronic nature ( electron withdrawing or donating group) and the position (o, m, p) of the substituents on the aromatic ring, a single beta-(E)-styrylsilanes was obtained in good to excellent yields. The regioselectivity of the H-Si bond addition was found to be governed by steric effects induced by the bulky Xphos ligand. A dramatic regioselectivity was also observed when functionalized terminal aliphatic alkynes were employed as a substrate and in these cases regioisomeric beta-(E)-vinylsilanes were generated with excellent selectivity. (c) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.05.028

文献信息

• Rhodium(I) Complexes with Ligands Based on N-Heterocyclic Carbene and Hemilabile Pyridine Donors as Highly <i>E</i> Stereoselective Alkyne Hydrosilylation Catalysts
  作者：Judith P. Morales-Cerón、Patricia Lara、Joaquín López-Serrano、Laura L. Santos、Verónica Salazar、Eleuterio Álvarez、Andrés Suárez

  DOI：10.1021/acs.organomet.7b00361

  日期：2017.7.10

  substitution at the 6-position of the pyridine donor serve as efficient E-selective alkyne hydrosilylation catalyst precursors. Particularly, when the steric hindrance of the picolyl fragment is increased, a catalyst precursor exhibiting high catalytic activities (TOF up to 500 h–1 at S/C ratios of 1000) and excellent E selectivities (E/α ratio ≥95/5) in the hydrosilylation of a series of aryl, alkyl, and

  包含吡啶供体6-位取代度不同的吡啶甲基-NHC（NHC = N-杂环卡宾）配体的阳离子铑（I）络合物可作为有效的E选择性炔烃氢化硅烷化催化剂前体。特别是，当甲基吡啶基片段的空间位阻增加时，催化剂前体表现出高催化活性（S / C比为1000时，TOF高达500 h –1）和极好的E选择性（E在一系列芳基，烷基和官能化的末端炔烃与碳-和烷氧基硅烷的氢化硅烷化反应中，获得了/α比≥95/ 5）。Rh配合物中的吡啶甲基-NHC配体由于吡啶片段的半不稳定配位作用而在溶液中表现出动态行为。初步的机理研究支持了由Rh配合物和硅烷低浓度生成的Rh甲硅烷基氢化物参与炔烃的氢化硅烷化反应，并与Chalk–Harrod型机理的假设相一致。
• 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。
• Dichloro(ethylenediamine)platinum(II), a water-soluble analog of the antitumor cisplatin, as a heterogeneous catalyst for a stereoselective hydrosilylation of alkynes under neat conditions
  作者：Jean Fotie、Mercy Enechojo Agbo、Fengrui Qu、Trevor Tolar

  DOI：10.1016/j.tetlet.2020.152300

  日期：2020.9

  hydrosilylation of internal and terminal alkynes under heterogeneous catalysis by dichloro(ethylenediamine)platinum(II) is discussed. This commercially available platinum complex operates under neat conditions at 90 °C, producing exclusively the (trans) Z-isomer with symmetrical internal alkynes, while terminal alkynes produce a mixture of α- and β(E)-hydrosilylated products. No β(Z)-hydrosilylated product was

  讨论了在二氯（乙二胺）铂（II）多相催化下内部和末端炔烃氢化硅烷化的立体选择方法。这种可商购的铂络合物在90°C的纯条件下运行，仅生成具有对称内部炔烃的（反式）Z-异构体，而末端炔烃则生成α-和β（E）-氢化硅烷化产物的混合物。在该研究中未观察到β（Z）-氢化硅烷化产物，并且α-和β（E）-氢化硅烷化产物之间的选择性似乎在一定程度上受氢硅烷性质的影响。该催化剂在克规模的条件下最多可循环使用五次，而催化活性没有任何损失。
• Platinum chloride/Xphos-catalyzed regioselective hydrosilylation of functionalized terminal arylalkynes
  作者：Abdallah Hamze、Olivier Provot、Jean-Daniel Brion、Mouâd Alami

  DOI：10.1016/j.tetlet.2008.02.060

  日期：2008.4

  Totally regioselective hydrosilylation of functionalized terminal arylalkynes was achieved using PtCl(2) associated with the air-stable and bulky Xphos ligand with various silanes. Regardless of the electronic nature of the substituents on the aromatic ring, a single beta-(E)-vinylsilane was obtained in excellent yields. (C) 2008 Elsevier Ltd. All rights reserved.
• A Rh(I) complex with an annulated N-heterocyclic carbene ligand for E-selective alkyne hydrosilylation
  作者：Akshi Tyagi、Suman Yadav、Prosenjit Daw、Chitrakar Ravi、Jitendra K. Bera

  DOI：10.1016/j.poly.2019.04.027

  日期：2019.11

  A Rh(I) complex supported by a fused pi-conjugated imidazo[1,2-a][1,8]naphthyridine-based N-heterocyclic carbene ligand with a Dipp attachment on the imidazole nitrogen has been synthesized and structurally characterized. The title complex is found to be an excellent catalyst for accessing E-vinylsilanes. The scope of the chemoselective hydrosilylation is examined for a range of terminal alkynes with silanes Et3SiH and (EtO)(3)SiH. (C) 2019 Elsevier Ltd. All rights reserved.