(E)-triethyl(2-methoxystyryl)silane | 866364-11-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (E)-triethyl(2-methoxystyryl)silane
• 英文别名: triethyl-[(E)-2-(2-methoxyphenyl)ethenyl]silane
• CAS: 866364-11-6
• 化学式: C₁₅H₂₄OSi
• 分子量: 248.44
• InChiKey: DQOFRRYFKHWLEC-OUKQBFOZSA-N

物化性质

• 沸点：
  310.3±25.0 °C(Predicted)
• 密度：
  0.911±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.76
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 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：

  三乙基乙烯基硅烷 、 2-溴苯甲醚 在 bis(η3-allyl-μ-chloropalladium(II)) sodium acetate 、 顺式,顺式,顺式-1,2,3,4-四[(二苯基膦)甲基]环戊烷 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 以54%的产率得到(E)-triethyl(2-methoxystyryl)silane
  参考文献：
  名称：

  Selective synthesis of (E)-triethyl(2-arylethenyl)silane derivatives by reaction of aryl bromides with triethyl vinylsilane catalysed by a palladium–tetraphosphine complex

  摘要：

  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.

  DOI：

  10.1016/j.jorganchem.2005.05.014

文献信息

• Reaction of hydrosilanes with alkynes catalyzed by gold nanoparticles supported on TiO2
  作者：Androniki Psyllaki、Ioannis N. Lykakis、Manolis Stratakis

  DOI：10.1016/j.tet.2012.08.021

  日期：2012.10

  Gold nanoparticles supported on TiO2 (0.8–1.4 mol %) catalyze the β-(E) regioselective hydrosilylation of a variety of functionalized terminal alkynes with alkylhydrosilanes in 1,2-dichloroethane (70 °C). The product yields are excellent, and the reaction times relatively short, while almost equimolar amounts of alkynes and hydrosilanes can be used. Minor side-products in up to 35% relative yield of

  负载在TiO 2（0.8-1.4 mol％）上的金纳米颗粒催化在1,2-二氯乙烷（70°C）中各种官能化的末端炔烃与烷基氢硅烷的β-（E）区域选择性氢化硅烷化。产物收率优异，反应时间相对较短，同时可以使用几乎等摩尔量的炔烃和氢硅烷。在受阻较少的氢化硅烷和炔烃的情况下，形成了副产物，其副产物的相对产率最高为顺式氧化（脱氢）二甲硅烷基化的35％，这是前所未有的反应途径。三乙氧基硅烷反应更快，除β-（E）加成产物，次要的α-氢化硅烷化区域异构体，相对产率高达15％。内部炔烃通常反应性较低甚至不反应。建议由载体稳定的阳离子Au（I）物种是反应性催化位点，在存在氢硅烷的情况下形成甲硅烷基-Au（III）-H（氢化硅烷化途径）或Au（III）-二甲硅烷基物种（脱氢二甲硅烷基化）途径）。关于氢化硅烷化的机理，动力学实验与反应速率确定步骤中三键的甲硅烷基碳金属化相一致。
• Palladium(II) Complexes of a Neutral CCC-Tris(N-heterocyclic carbene) Pincer Ligand: Synthesis and Catalytic Applications
  作者：David Rendón-Nava、Deyanira Angeles-Beltrán、Arnold L. Rheingold、Daniel Mendoza-Espinosa

  DOI：10.1021/acs.organomet.1c00324

  日期：2021.7.12

  tris-azolium precursor 1 with palladium acetate under thermal conditions provided a CCC-pincer palladium(II) complex (2) bearing three NHCs (one imidazolylidene and two triazolylidenes) and one iodide ligand. Further treatment of complex 2 with an excess of AgSbF6 generates tris(carbene) dicationic palladium complex 3 in which the iodine ligands are exchanged with SbF6 anions and the metal center is stabilized

  在热条件下用乙酸钯处理三唑鎓前体1提供了带有三个 NHC（一个咪唑亚基和两个三唑基亚基）和一个碘化物配体的 CCC-钳状钯 (II) 复合物 ( 2 )。用过量的 AgSbF 6进一步处理配合物2生成三（卡宾）双阳离子钯配合物3，其中碘配体与 SbF 6阴离子交换，金属中心由一个乙腈配体稳定。配合物2和3在几个交叉偶联反应中进行了测试，显示在低催化剂负载和温和反应条件下的高转化率。此外，复合体2和3在末端炔烃的氢化硅烷化中表现良好，对E-异构体具有良好的选择性。
• Markovnikov Hydrosilylation of Alkynes with Tertiary Silanes Catalyzed by Dinuclear Cobalt Carbonyl Complexes with NHC Ligation
  作者：Dongyang Wang、Yuhang Lai、Peng Wang、Xuebing Leng、Jie Xiao、Liang Deng

  DOI：10.1021/jacs.1c06583

  日期：2021.8.18

  with PhC≡CH and HSiEt3 can furnish the dinuclear cobalt alkyne and mononuclear cobalt silyl complexes [(IPr)(CO)2Co(μ–η2:η2-HCCPh)Co(CO)3], [(IPr)(CO)2Co(μ-η2:η2-HCCPh)Co(CO)2(IPr)], and [(IPr)Co(CO)3(SiEt3)], respectively. Both dicobalt bridging alkyne complexes can react with HSiEt3 to yield α-triethylsilyl styrene and effect the catalytic Markovnikov hydrosilylation reaction. However, the mono(NHC)

  炔烃的金属催化氢化硅烷化是制备乙烯基硅烷的理想原子经济方法，乙烯基硅烷是有机合成和有机硅工业中的有用试剂。尽管通过炔烃的金属催化氢化硅烷化反应制备 β-乙烯基硅烷已取得巨大成功，但报道的用于合成 α-乙烯基硅烷的金属催化反应存在底物范围窄和/或选择性差的问题。在此，我们使用羰基N-杂环卡宾 (NHC) 配合物 [(IPr) 2 Co 2 (CO) 6] (IPr = 1,3-二(2,6-二异丙基苯基)咪唑-2-亚基)作为催化剂。这种钴催化剂影响烷基和芳基取代的末端炔烃与各种具有良好官能团相容性的叔硅烷的氢化硅烷化，从而提供具有高产率和高α / β选择性的α-乙烯基硅烷。机理研究表明[(IPr) 2 Co 2 (CO) 6 ]与PhC≡CH和HSiEt 3的化学计量反应可以提供双核钴炔和单核钴甲硅烷基配合物[(IPr)(CO) 2 Co(μ– η 2 :η 2 -HCCPh)Co(CO) 3
• A recyclable and reusable K₂PtCl₄/Xphos-SO₃Na/PEG-400/H₂O system for highly regio- and stereoselective hydrosilylation of terminal alkynes
  作者：Caifeng Xu、Bin Huang、Tao Yan、Mingzhong Cai

  DOI：10.1039/c7gc02823g

  日期：——

  K2PtCl4/Xphos-SO3Na in a mixture of poly(ethylene glycol) (PEG-400) and water is shown to be a highly regio- and stereoselective catalyst for the hydrosilylation of terminal alkynes with hydrosilanes. The reaction could be conducted under mild conditions, yielding a variety of functionalized β-(E)-vinylsilanes in good to excellent yields with a total β-(E)-selectivity. The isolation of the products

  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。
• 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。