(E)-3-(phenylsilyl)hex-3-ene | 1584730-79-9

• 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: (E)-3-(phenylsilyl)hex-3-ene
• 英文别名: (E)-hex-3-en-3-yl(phenyl)silane；[(E)-hex-3-en-3-yl]-phenylsilane
• CAS: 1584730-79-9
• 化学式: C₁₂H₁₈Si
• 分子量: 190.36
• InChiKey: YDSNKSHJMZVGAP-DHZHZOJOSA-N

物化性质

• 沸点：
  250.0±9.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.18
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  3-己炔 、 苯硅烷 在 (2,5-bis(dicyclohexylphosphinomethyl)pyrrolyl)bis((trimethylsilyl)methyl)scandium 作用下， 以 氘代苯 为溶剂， 反应 60.0h， 以98%的产率得到(E)-3-(phenylsilyl)hex-3-ene
  参考文献：
  名称：

  NP和钇的PNP配合物对烯烃和炔烃的加氢和硅氢化反应的选择性催化

  摘要：

  研究了由单阴离子PNP配体支撑的和钇同系配合物作为烯烃加氢和硅氢化反应以及炔烃半氢化和半硅氢化反应的催化剂。已发现钇同系物在所有情况下均具有更高的活性，但是这种更高的活性伴随着更快速的催化剂分解，因此，对于某些与the催化剂的反应，其总收率更高。计算表明该反应可以通过烷基络合物的σ-键复分解进行，以形成烯烃/炔烃插入其中的金属氢化物中间体。

  DOI：

  10.1039/c7cc06417a

文献信息

• Highly Regio- and Stereoselective Markovnikov Hydrosilylation of Alkynes Catalyzed by High-Nuclearity {Co₁₄} Clusters
  作者：Jun-Song Jia、Yan Cao、Tai-Xue Wu、Ye Tao、Ying-Ming Pan、Fu-Ping Huang、Hai-Tao Tang

  DOI：10.1021/acscatal.1c01996

  日期：2021.6.18

  C1 exhibited highly regio- and stereoselective hydrosilylation of alkynes with primary and secondary silane to produce α-vinylsilanes. More importantly, C1 shows high regioselectivity for electronically unbiased alkyl alkynes, and the α-selectivity of some alkyl alkynes has not been achieved in previous reports. Leaching tests and reusability proved that the reaction is a heterogeneous process.

  这项工作开发了C1-C3 的三个高核 Co 14 } 簇，其内部 [Co 8 ] 主链由六个环境 CoCl 2物种固定。催化剂C1表现出炔烃与伯硅烷和仲硅烷的高度区域和立体选择性氢化硅烷化，以生产 α-乙烯基硅烷。更重要的是，C1对电子无偏的烷基炔烃显示出高区域选择性，而一些烷基炔烃的α-选择性在之前的报道中尚未实现。浸出试验和可重用性证明该反应是一个非均相过程。
• Efficient and selective alkene hydrosilation promoted by weak, double Si–H activation at an iron center
  作者：Patrick W. Smith、Yuyang Dong、T. Don Tilley

  DOI：10.1039/d0sc01749c

  日期：——

  Cationic iron complexes [Cp*(ⁱPr₂MeP)FeH₂SiHR]⁺, generated and characterized in solution, are very efficient catalysts for the hydrosilation of terminal alkenes and internal alkynes by primary silanes at low catalyst loading (0.1 mol%) and ambient temperature.

  阳离子铁配合物[Cp*(ⁱPr₂MeP)FeH₂SiHR]⁺在溶液中生成并表征，对末端烯烃和内部炔烃的氢硅烷化反应具有很高的催化效率，且在低催化剂负载量（0.1 mol%）和室温下表现出良好的催化活性。
• An NNN-Pincer-Cobalt Complex Catalyzed Highly Markovnikov-Selective Alkyne Hydrosilylation
  作者：Shaochun Zhang、Jessica Juweriah Ibrahim、Yong Yang

  DOI：10.1021/acs.orglett.8b02746

  日期：2018.10.5

  A new NNN pincer (amine–pyridine–imine, API) cobalt complex, which is bench-stable and is applicable for the highly efficient and regioselective hydrosilylation of terminal alkynes, is developed. A broad set of α-vinylsilanes was successfully synthesized in good to high yields with up to 98/2 Markovnikov regioselectivity. This protocol can be readily scaled up for gram-scale synthesis and demonstrates

  开发了一种新型的NNN钳形（胺-吡啶-亚胺，API）钴复合物，该复合物具有台式稳定性，适用于末端炔烃的高效和区域选择性氢化硅烷化。成功地以高至高收率和高达98/2的马尔可夫尼科夫区域选择性合成了多种α-乙烯基硅烷。该方案可以很容易地按比例放大以进行克级合成，并证明迄今为止，最有效的炔烃钴催化氢化硅烷化反应的周转频率高达126 720 h –1。
• Iron-Catalysed Chemo-, Regio-, and Stereoselective Hydrosilylation of Alkenes and Alkynes using a Bench-Stable Iron(II) Pre-Catalyst
  作者：Mark D. Greenhalgh、Dominik J. Frank、Stephen P. Thomas

  DOI：10.1002/adsc.201300827

  日期：2014.2.10

  AbstractThe chemo‐, regio‐, and stereoselective iron‐catalysed hydrosilylation of alkenes and alkynes with excellent functional group tolerance is reported (34 examples, 41–96% yield). The catalyst and reagents are commercially available and easy to handle, with the active iron catalyst being generated in situ, thus providing a simple and practical methodology for iron‐catalysed hydrosilylation. The silane products can be oxidised to the anti‐Markovnikov product of olefin hydration, and the one‐pot iron‐catalysed hydrosilylation–oxidation of olefins to give silane(di)ols directly is also reported. The iron pre‐catalyst was used at loadings as low as 0.07 mol%, and displayed catalyst turnover frequencies (TOF) approaching 60,000 mol h−1. Initial mechanistic studies indicate an iron(I) active catalyst.magnified image