methyl (E)-4-[2-(triethylsilyl)vinyl]benzoate | 866363-95-3

• 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: methyl (E)-4-[2-(triethylsilyl)vinyl]benzoate
• 英文别名: methyl 4-[(E)-2-triethylsilylethenyl]benzoate
• CAS: 866363-95-3
• 化学式: C₁₆H₂₄O₂Si
• 分子量: 276.451
• InChiKey: PSWAMGSQQSQIJS-OUKQBFOZSA-N

物化性质

• 沸点：
  349.6±35.0 °C(Predicted)
• 密度：
  0.964±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.53
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  三乙基硅烷 、 4-乙炔基苯甲酸甲酯 在 C₆₀H₈₄Cl₂O₆P₂PtS₂^(2-)*2Na⁽¹⁺⁾ 作用下， 以 水 为溶剂， 反应 6.0h， 以87%的产率得到methyl (E)-4-[2-(triethylsilyl)vinyl]benzoate
  参考文献：
  名称：

  可回收和可重复使用的K 2 PtCl 4 / Xphos-SO 3 Na / PEG-400 / H 2 O系统，用于末端炔烃的高度区域选择性和立体选择性氢化硅烷化

  摘要：

  在聚（乙二醇）（PEG-400）和水的混合物中，K 2 PtCl 4 / Xphos-SO 3 Na被证明是高度炔和立体选择性的催化剂，用于末端炔烃与氢硅烷的硅氢化反应。该反应可以在温和的条件下进行，以良好的至优异的产率产生各种官能化的β-（E）-乙烯基硅烷，并具有总的β-（E）-选择性。产物的分离很容易通过环己烷萃取，更重要的是，在PEG-400 / H 2中用昂贵的K 2 PtCl 4和Xphos-SO 3 Na萃取。O系统可以轻松回收再利用至少八次，而不会损失任何催化活性。

  DOI：

  10.1039/c7gc02823g

文献信息

• Regiochemical Aspects of the Platinum Oxide Catalyzed Hydrosilylation of Alkynes
  作者：Mouâd Alami、Abdallah Hamze、Olivier Provot、Jean-Daniel Brion

  DOI：10.1055/s-2007-983742

  日期：2007.7

  The platinum-catalyzed hydrosilylation of unsymmetrical substituted arylalkynes with various hydrosilanes was investigated and the reaction selectivity of various para-substituted substrates was compared with that of their corresponding ortho-substituted derivatives. We showed that heterogeneous platinum oxide is a very efficient catalyst for such hydrosilylations and that H-Si bond addition proceeds in a stereoselective cis-fashion. The regioselectivity was found to be under the control of the ortho-substituent rather than due to the nature of the platinum catalyst. Aryl­alkynes with an ortho-substituent provided predominantly to exclusively α-selectivity, regardless of the electronic nature of the substituent. The precise contributions of steric, electronic, and coordinative factors controlling the regioselectivity of the H-Si bond addition are discussed.

  对不对称取代的芳基炔与各种氢硅烷的铂催化氢硅化反应进行了研究，并比较了不同对位取代底物的反应选择性与其相应的邻位取代衍生物的反应选择性。我们展示了异相铂氧化物是一种高效的催化剂用于此类氢硅化反应，且H-Si键的加成以立体选择性的顺式方式进行。区域选择性被发现是由邻位取代基控制，而不是由铂催化剂的性质决定。带有邻位取代基的芳基炔提供了主要到完全的α-选择性，无论取代基的电子性质如何。我们还讨论了影响H-Si键加成的区域选择性的立体、电子和配位因素的精确贡献。
• FeCl2/DTBP: An efficient and highly E-selective cross - coupling of silanes with styrene and its derivatives
  作者：Rui Xu、Chun Cai

  DOI：10.1016/j.catcom.2017.12.023

  日期：2018.3

  An efficient FeCl2-catalyzed cross-coupling of silanes with styrene and its derivatives using DTBP as oxidant for selective synthesis of vinylsilanes was developed. This method presented an inexpensive, non-toxic and environmentally benign catalytic system with an appropriate substrate scope. This approach is E-specific and produced important classes of vinylsilanes in good yields. Control experiments

  开发了一种有效的FeCl 2催化的硅烷与苯乙烯及其衍生物的交叉偶联方法，该方法使用DTBP作为氧化剂选择性合成乙烯基硅烷。该方法提供了一种廉价，无毒且对环境无害的催化体系，并具有适当的底物范围。这种方法是E特定的，并且以高收率生产了重要种类的乙烯基硅烷。对照实验表明该反应可以通过自由基途径进行。
• 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.
• Xphos ligand and platinum catalysts: A versatile catalyst for the synthesis of functionalized β-(E)-vinylsilanes from terminal alkynes
  作者：Abdallah Hamze、Olivier Provot、Jean-Daniel Brion、Mouâd Alami

  DOI：10.1016/j.jorganchem.2008.05.028

  日期：2008.8

  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.
• Selective synthesis of (E)-triethyl(2-arylethenyl)silane derivatives by reaction of aryl bromides with triethyl vinylsilane catalysed by a palladium–tetraphosphine complex
  作者：Ahmed Battace、Touriya Zair、Henri Doucet、Maurice Santelli

  DOI：10.1016/j.jorganchem.2005.05.014

  日期：2005.8

  Cis, cis, cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane/0.5[PdCI(C3H5)](2) system catalyses the Heck reaction of vinylsilane derivatives with a range of aryl bromides with high ratio substrate/catalyst in good yields. The formation of mixtures of styrene, (E)-triethyl(2-arylethenyl)sitane and triethyl(1-arylethenyl)silane derivatives was observed in some cases. Very high selectivities (up to 100%) in favour of the formation of (E)-triethyl(2-arylethenyl)silane derivatives were obtained in the presence of sodium acetate as base. With other bases such as potassium carbonate, the formation of large amounts of styrene derivatives was observed. The reaction tolerates several functions such as fluoro, trifluoromethyl, methoxy, dimethylamino, acetyl, formyl, benzoyl, carboxylate, nitro or nitrile. Moreover, turnover numbers up to 10,000 can be obtained for this reaction. (c) 2005 Elsevier B.V. All rights reserved.