2-(vinyldimethylsilyl)thiophene | 78599-06-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 2-(vinyldimethylsilyl)thiophene
• 英文别名: dimethyl(thiophen-2-yl)(vinyl)silane；Ethenyl-dimethyl-thiophen-2-ylsilane
• CAS: 78599-06-1
• 化学式: C₈H₁₂SSi
• 分子量: 168.335
• InChiKey: AYCAFFFLMKTXIC-UHFFFAOYSA-N

物化性质

• 沸点：
  190.5±13.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.39
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-碘三氟甲苯 、 2-(vinyldimethylsilyl)thiophene 在 palladium diacetate 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以90%的产率得到对三氟甲基苯乙烯
  参考文献：
  名称：

  Alkenyldimethyl(2-thienyl)silanes, Excellent Coupling Partner for the Palladium-Catalyzed Cross-Coupling Reaction

  摘要：

  在烯基硅烷的硅原子上引入 2-噻吩基团，可促进与芳基卤化物在四丁基氟化铵和钯催化剂的介导下发生交叉偶联反应。反应在极其温和的条件下进行，并以高产率得到芳基烯烃。

  DOI：

  10.1246/cl.2002.138
• 作为产物：
  描述：

  甲基碘化镁 、 (2-thienyl)vinyldichlorosilane 以 乙醚 为溶剂， 反应 1.0h， 以33%的产率得到2-(vinyldimethylsilyl)thiophene
  参考文献：
  名称：

  Synthesis of Thiophene Derivatives Bearing a Silicon Atom

  摘要：

  Synthesis of thiophene derivatives containing a silicon atom is described. Silylation of 2-thienylmethyl chloride (12) with trichlorovinylsilane or chloro(chloromethyl)dimethylsilane was accomplished by addition of 12 to a mixture of Mg and the former reagent in THF or by addition of a mixture of 12 and the latter reagent to a mixture of Mg in THF to give dichloro(2-thienylmethyl)vinylsilane (13) or chloromethyl(dimethyl)(2-thienylmethyl) (18). The Grignard reagent (19) of 18 reacted with carbon dioxide, dimethyl carbonate or benzaldehyde to produce dimethyl(2-thienylmethyl)silylacetic acid (20), methyl dimethyl(2-thienylmethyl)silylacetate (21) or 2'-[dimethyl(2-thienylmethyl)silyl]-1'-phenylethanol (22).

  DOI：

  10.3987/com-96-s51

文献信息

• Photo-induced Decarboxylative Heck-Type Coupling of Unactivated Aliphatic Acids and Terminal Alkenes in the Absence of Sacrificial Hydrogen Acceptors
  作者：Hui Cao、Heming Jiang、Hongyu Feng、Jeric Mun Chung Kwan、Xiaogang Liu、Jie Wu

  DOI：10.1021/jacs.8b11218

  日期：2018.11.28

  boronates are among the most versatile building blocks that can be found in every sector of chemical science. We herein report a noble-metal-free method of accessing such olefins through a photo-induced decarboxylative Heck-type coupling using alkyl carboxylic acids, one of the most ubiquitous building blocks, as the feedstocks. This transformation was achieved in the absence of external oxidants through

  1,2-二取代的烯烃，如乙烯基芳烃、乙烯基硅烷和乙烯基硼酸酯，是化学科学各个领域中最通用的结构单元。我们在此报告了一种无贵金属的方法，该方法使用烷基羧酸（最普遍的结构单元之一）作为原料，通过光诱导脱羧 Heck 型偶联获得此类烯烃。这种转变是在没有外部氧化剂的情况下通过有机光氧化还原催化剂和钴肟催化剂的协同组合实现的，H2 和 CO2 作为唯一的副产物。控制实验和 DFT 计算都支持基于自由基的机制，最终导致开发出脂肪族羧酸、丙烯酸酯和乙烯基芳烃的选择性三组分偶联。
• Hydrosilylation of unsaturated compounds with 5-dimethylsilylfurfural diethyl acetal
  作者：E. Lukevics、L. E. Demicheva、N. P. Yerchak、Yu. Popelis

  DOI：10.1007/bf00697047

  日期：1993.10

  Hydrosilylation of terminal acetylenes, HC≡CR (R = CMe3,n-C7H15, SiMe3, Ph, COOEt, CH2N(CH2)4, and CH2N(CH2)5) with 5-dimethylsilylfurfural diethyl acetal (1) gives a mixture of products of bothtrans-β- and α-addition. When R = CMe3 or SiMe3, the reaction proceeds regio- and stereospecifically to give only thetrans-β-derivatives. The formation of β-adducts is favored by pronounced electron-donating

  末端乙炔、HC≡CR（R = CMe3、n-C7H15、SiMe3、Ph、COOEt、CH2N(CH2)4 和 ( )5）与 5-二甲基甲硅烷基糠醛二乙缩醛 (1) 的氢化硅烷化得到产物混合物反式-β-和α-加成。当 R = CMe3 或 SiMe3 时，反应进行区域定向和立体定向，仅产生反式-β-衍生物。明显的给电子取代基和 Cα 原子的位阻有利于 β-加合物的形成。末端烯烃，H2C=CHR（R = CN、 ( )4、 ( )5、SiMe3、SiMe(α-呋喃基)2、SiMe2(α-呋喃基)、SiMe2(α-噻吩基)和SiMe2( 5-氯-2-噻吩基))，与硅烷1反应只得到β-加成产物；1与H2C=CH HC6H13-n的反应得到β-​​和α-加合物的比例为1.8:1的混合物。
• Hydroaminoalkylation/Buchwald‐Hartwig Amination Sequences for the Synthesis of Novel Thieno‐ or Benzothieno‐Annulated Tetrahydropyridines, Tetrahydroazasilines, and Tetrahydroazasilepines
  作者：Michael Warsitz、Stefan H. Rohjans、Marc Schmidtmann、Sven Doye

  DOI：10.1002/ejoc.202001523

  日期：2021.2.5

  Hydroaminoalkylation reactions of 2‐allyl‐, 2‐allyldimethylsilyl‐, or 2‐dimethyl(vinyl)silyl‐substituted 3‐bromothiophenes or 3‐bromobenzothiophenes with secondary amines deliver the branched or the linear addition products with high regioselectivity. A combination of this reaction with a subsequent intramolecular Buchwald‐Hartwig amination results in several one‐pot processes that give direct access

  2-仲烯丙基，2-烯丙基二甲基甲硅烷基或2-二甲基（乙烯基）甲硅烷基取代的3-溴噻吩或3-溴苯并噻吩与仲胺的加氢氨基烷基化反应可提供具有高区域选择性的支链或线性加成产物。该反应与随后的分子内Buchwald-Hartwig胺化反应相结合，产生了多个一锅法，可直接进入结构新颖的噻吩或苯并噻吩环化的6元和7元杂环。
• Regioselective Hydroalkylation of Vinyl- and Allylsilanes as Well as Vinylgermanes under Ni–H Catalysis
  作者：Daniel Brösamlen、Martin Oestreich

  DOI：10.1021/acs.orglett.3c01881

  日期：2023.7.21

  A Ni–H-catalyzed hydroalkylation of vinylsilanes and -germanes as well as allylsilanes with unactivated alkyl iodides is reported. Unlike related reactions of styrene or vinyl boronate esters, the addition across the C–C double bond proceeds with anti-Markovnikov selectivity to deliver the linear regioisomer. Mechanistic control experiments support a radical mechanism, and a competition experiment

  报道了乙烯基硅烷和α-锗烷以及烯丙基硅烷与未活化的烷基碘的 Ni-H 催化加氢烷基化反应。与苯乙烯或乙烯基硼酸酯的相关反应不同，C-C 双键上的加成反应具有反马尔可夫尼科夫选择性，从而产生线性区域异构体。机械控制实验支持一种激进的机制，而竞争实验表明，化学选择性有利于乙烯基而不是烯丙基。
• Highly stereoselective synthesis of novel trans-thiophenylene-silylene-vinylene-arylene molecular and macromolecular compounds
  作者：Monika Ludwiczak、Mariusz Majchrzak、Bogdan Marciniec、Maciej Kubicki

  DOI：10.1016/j.jorganchem.2011.01.020

  日期：2011.4

  Novel stereoregular molecular compounds 8-13 containing thiophenylene-silylene-vinylene-phenylene units have been synthesised via highly effective silylative coupling of styrene and 1,4-divinylbenzene (7) with respective vinylsilylthiophenes (3, 4) and bis(vinylsilyl) thiophenes (5, 6) catalyzed by RuHClCO (PCy(3))(2). Respective copolymers (14, 15) were produced via silylative copolycondensation of 5 and 6 with 7. All products were isolated and characterised by NMR, MS, HRMS and two of them 10 and 11 by X-ray method. Catalytic study as well as stoichiometric reactions of Ru-H (1) with 2-(vinylsilyl) thiophene (3) and Ru-Si (16) with styrene confirmed the mechanism of the silylative coupling olefins with vinylsilicon compounds. (C) 2011 Elsevier B.V. All rights reserved.