pentamethylphenylethene | 13324-25-9

• 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: pentamethylphenylethene
• 英文别名: 1,2,3,4,5-pentamethyl-6-vinylbenzene；vinylpentamethylbenzene；VPMB；1-Ethenyl-2,3,4,5,6-pentamethylbenzene
• CAS: 13324-25-9
• 化学式: C₁₃H₁₈
• 分子量: 174.286
• InChiKey: UFMLLTODLZCTMW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 海关编码：
  2902909090

反应信息

• 作为反应物：
  描述：

  三乙基硅烷 、 pentamethylphenylethene 在 羰基镁 、 N,N-bis(diphenylphosphino)isopropylamine 作用下， 反应 24.0h， 以82%的产率得到(E)-triethyl(2,3,4,5,6-pentamethylstyryl)silane
  参考文献：
  名称：

  锰催化烯烃的发散硅烷化反应

  摘要：

  过渡金属催化的、氧化还原中性的烯烃脱氢硅烷化是有机合成中长期存在的挑战，目前的方法存在选择性低和范围窄的问题。在这项研究中，我们报告了锰催化的烯烃脱氢硅烷化和氢化硅烷化的通用且简单的方法，使用配体调节的金属自由基反应策略，以 Mn 2 (CO) 10作为催化剂前体。这使得烯烃和硅烷比例为 1:1 的多功能性和可控选择性成为可能，并且使用复杂的烯烃和轻质烯烃证明了该方法的合成稳健性和实用性。使用密度泛函理论计算研究了反应的选择性，显示了iPrPNP 配体有利于脱氢硅烷化，而 JackiePhos 配体有利于氢化硅烷化。该反应是氧化还原中性和原子经济的，具有广泛的底物范围和优异的官能团耐受性，适用于克级的各种合成应用。

  DOI：

  10.1038/s41557-020-00589-8
• 作为产物：
  描述：

  五甲基苯 、 乙炔 在 四氟硼酸-二乙醚络合物 、 (Z)-[Pt(PNP)(CHCHC₆Me₅)]BF₄ 作用下， 以 二氯甲烷-D2 为溶剂， 反应 1.5h， 生成 pentamethylphenylethene
  参考文献：
  名称：

  Mechanistic Studies on Platinum(II) Catalyzed Hydroarylation of Alkynes

  摘要：

  The dicationic acetylene platinum(II) complex [Pt(PNP)(C2H2)](BF4)(2) (PNP = 2,6-bis(diphenylphosphinomethyl)pyridine) was generated in situ by ligand substitution from the ethylene complex [Pt(PNP)(C2H4)](BF4)(2) and was reacted with a series of arenes at low temperature. Only electron-rich arenes added across the coordinated C-C triple bond and gave the corresponding arylalkenyl complexes (E)-[Pt(PNP)(CH=CHAr)]BF4 (Ar = C6Me5, C6H2Me3-2,4,6, C6H3Me2-2,6, C6H3Me2-2,4). A slow E-Z isomerization of the arylalkenyl complexes was observed. Single-crystal X-ray structure analyses were obtained for both E and Z isomers of the pentamethylbenzene derivative. The E isomers of [Pt(PNP)(CH=CHAr)]BF4 (Ar = C6Me5, C6H2Me3-2,4,6) reacted with excess HBF4 center dot Et2O to give the corresponding arylalkene complexes [Pt(PNP)(CH2=CHAr)](BF4)(2), whereas the Z isomers did not undergo immediate protonolysis. Using (E)-[Pt(PNP)(CD=CDC6Me5)]BF4 it was shown that the stereochemistry of the C-C double bond in the protonolysis product depends on the nature of the acid anion HX (X- = Cl-, BF4-). The catalytic hydroarylation was studied in solution by NMR spectroscopy. The reaction studies provide a more refined view of the individual steps proposed for the Friedel-Crafts type mechanism of the Pt-II-catalyzed intermolecular hydroarylation of alkynes.

  DOI：

  10.1021/om5003123

文献信息

• Photoredox Divergent 1,2-Difunctionalization of Alkenes with <i>gem</i>-Dibromides
  作者：Jian Cheng、Yixiang Cheng、Jin Xie、Chengjian Zhu

  DOI：10.1021/acs.orglett.7b03371

  日期：2017.12.1

  The redox neutral photocatalytic divergent radical 1,2-difunctionalization of a wide array of structurally varied alkenes with gem-dibromides is presented. On the basis of the electronic effect of alkenes, predictable 1,2-carboxygenation and 1,2-carbohalogenation of alkenes are readily available regardless of steric effect. This protocol affords a practical approach to the biologically important furan skeleton. It is distinguished by good regioselectivity, good functional group compatibility, and late-stage modification and thus signifies an important step forward to divergent radical difunctionalization of alkenes.
• Mechanistic Studies on Platinum(II) Catalyzed Hydroarylation of Alkynes
  作者：Christine Hahn、Mayra Miranda、Nagendra P. B. Chittineni、Trent A. Pinion、Ricardo Perez

  DOI：10.1021/om5003123

  日期：2014.6.23

  The dicationic acetylene platinum(II) complex [Pt(PNP)(C2H2)](BF4)(2) (PNP = 2,6-bis(diphenylphosphinomethyl)pyridine) was generated in situ by ligand substitution from the ethylene complex [Pt(PNP)(C2H4)](BF4)(2) and was reacted with a series of arenes at low temperature. Only electron-rich arenes added across the coordinated C-C triple bond and gave the corresponding arylalkenyl complexes (E)-[Pt(PNP)(CH=CHAr)]BF4 (Ar = C6Me5, C6H2Me3-2,4,6, C6H3Me2-2,6, C6H3Me2-2,4). A slow E-Z isomerization of the arylalkenyl complexes was observed. Single-crystal X-ray structure analyses were obtained for both E and Z isomers of the pentamethylbenzene derivative. The E isomers of [Pt(PNP)(CH=CHAr)]BF4 (Ar = C6Me5, C6H2Me3-2,4,6) reacted with excess HBF4 center dot Et2O to give the corresponding arylalkene complexes [Pt(PNP)(CH2=CHAr)](BF4)(2), whereas the Z isomers did not undergo immediate protonolysis. Using (E)-[Pt(PNP)(CD=CDC6Me5)]BF4 it was shown that the stereochemistry of the C-C double bond in the protonolysis product depends on the nature of the acid anion HX (X- = Cl-, BF4-). The catalytic hydroarylation was studied in solution by NMR spectroscopy. The reaction studies provide a more refined view of the individual steps proposed for the Friedel-Crafts type mechanism of the Pt-II-catalyzed intermolecular hydroarylation of alkynes.
• Manganese-catalysed divergent silylation of alkenes
  作者：Jie Dong、Xiang-Ai Yuan、Zhongfei Yan、Liying Mu、Junyang Ma、Chengjian Zhu、Jin Xie

  DOI：10.1038/s41557-020-00589-8

  日期：2021.2

  challenge in organic synthesis, with current methods suffering from low selectivity and narrow scope. In this study, we report a general and simple method for the manganese-catalysed dehydrosilylation and hydrosilylation of alkenes, with Mn2(CO)10 as a catalyst precursor, by using a ligand-tuned metalloradical reactivity strategy. This enables versatility and controllable selectivity with a 1:1 ratio

  过渡金属催化的、氧化还原中性的烯烃脱氢硅烷化是有机合成中长期存在的挑战，目前的方法存在选择性低和范围窄的问题。在这项研究中，我们报告了锰催化的烯烃脱氢硅烷化和氢化硅烷化的通用且简单的方法，使用配体调节的金属自由基反应策略，以 Mn 2 (CO) 10作为催化剂前体。这使得烯烃和硅烷比例为 1:1 的多功能性和可控选择性成为可能，并且使用复杂的烯烃和轻质烯烃证明了该方法的合成稳健性和实用性。使用密度泛函理论计算研究了反应的选择性，显示了iPrPNP 配体有利于脱氢硅烷化，而 JackiePhos 配体有利于氢化硅烷化。该反应是氧化还原中性和原子经济的，具有广泛的底物范围和优异的官能团耐受性，适用于克级的各种合成应用。