7-(trimethylsilyl)-5-heptenenitrile | 119554-61-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 7-(trimethylsilyl)-5-heptenenitrile
• 英文别名: 7-(Trimethylsilyl)hept-5-enenitrile；7-trimethylsilylhept-5-enenitrile
• CAS: 119554-61-9
• 化学式: C₁₀H₁₉NSi
• 分子量: 181.353
• InChiKey: FUPQWABSPWXMHG-UHFFFAOYSA-N

物化性质

• 沸点：
  255.1±33.0 °C(Predicted)
• 密度：
  0.838±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.57
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  7-(trimethylsilyl)-5-heptenenitrile 在 四丁基氟化铵 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 16.33h， 生成 (1S,2R)-2-ethenyl-1-(4-fluorophenyl)cyclopentan-1-ol
  参考文献：
  名称：

  Intramolecular Cyclization of Tethered Phenyl Ketones. Complementary Stereochemical Results Arising from the Indium-Promoted Ring Closure of Allyl Bromides and the Fluoride Ion-Induced Desilylation of Allylsilanes

  摘要：

  dThe intramolecular indium-promoted cyclization of 4'-substituted (Z)- and (E)-7-bromo-5-heptenophenones has been examined in aqueous tetrahydrofuran. In every instance, ring closure occurred to deliver the syn-2-vinylcyclopentanol exclusively. The corresponding allylsilanes have been prepared as well, and the course of their fluoride ion-induced cyclization was also studied. In these systems, a kinetic bias for formation of the anti-2-vinylcyclopentanol is observed, although not with the same exclusivity. Accordingly, complementarity in product diastereoselectivity can be realized in purposeful fashion. The data acquired in this investigation suggest that the indium-catalyzed reactions involve intramolecularly coordinated transition states where development of a cis 5/6-bicyclic framework is most energetically feasible. In contrast, the silanes appear to utilize open-chain antiperiplanar transition states. While the latter are not particularly sensitive to double-bond geometry, they are responsive to steric compression involving the aryl group.

  DOI：

  10.1021/jo981683s
• 作为产物：
  描述：

  (6-hydroxyhex-2-enyl)trimethylsilane 在 咪唑 、 碘 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 0.33h， 生成 7-(trimethylsilyl)-5-heptenenitrile
  参考文献：
  名称：

  Intramolecular Cyclization of Tethered Phenyl Ketones. Complementary Stereochemical Results Arising from the Indium-Promoted Ring Closure of Allyl Bromides and the Fluoride Ion-Induced Desilylation of Allylsilanes

  摘要：

  dThe intramolecular indium-promoted cyclization of 4'-substituted (Z)- and (E)-7-bromo-5-heptenophenones has been examined in aqueous tetrahydrofuran. In every instance, ring closure occurred to deliver the syn-2-vinylcyclopentanol exclusively. The corresponding allylsilanes have been prepared as well, and the course of their fluoride ion-induced cyclization was also studied. In these systems, a kinetic bias for formation of the anti-2-vinylcyclopentanol is observed, although not with the same exclusivity. Accordingly, complementarity in product diastereoselectivity can be realized in purposeful fashion. The data acquired in this investigation suggest that the indium-catalyzed reactions involve intramolecularly coordinated transition states where development of a cis 5/6-bicyclic framework is most energetically feasible. In contrast, the silanes appear to utilize open-chain antiperiplanar transition states. While the latter are not particularly sensitive to double-bond geometry, they are responsive to steric compression involving the aryl group.

  DOI：

  10.1021/jo981683s

文献信息

• Preparation of allylsilanes via cross-metathesis
  作者：William E. Crowe、Daniel R. Goldberg、Zhijia J. Zhang

  DOI：10.1016/0040-4039(96)00230-4

  日期：1996.3

  Allylsilanes are prepared by simple metathetical cross-coupling of terminal olefins with allyltrimethylsilane. Allytrimethylsilane coupling with π-substituted terminal olefins (styrenes, 1-phenyl-1,3-butadiene, and acrylonitrile) proceeds in excellent yield and very high selectivity. Lower, but still useful, selectivities are observed for allyltrimethylsilane/alkyl olefin cross-metathesis reactions

  烯丙基硅烷是通过末端烯烃与烯丙基三甲基硅烷的简单易位交叉偶联制备的。烯丙基三甲基硅烷与π-取代的末端烯烃（苯乙烯，1-苯基-1,3-丁二烯和丙烯腈）偶合，具有极好的收率和很高的选择性。对于烯丙基三甲基硅烷/烷基烯烃交叉复分解反应，观察到较低但仍有用的选择性。
• Intramolecular Cyclization of Tethered Phenyl Ketones. Complementary Stereochemical Results Arising from the Indium-Promoted Ring Closure of Allyl Bromides and the Fluoride Ion-Induced Desilylation of Allylsilanes
  作者：Leo A. Paquette、José L. Mendez-Andino

  DOI：10.1021/jo981683s

  日期：1998.11.1

  dThe intramolecular indium-promoted cyclization of 4'-substituted (Z)- and (E)-7-bromo-5-heptenophenones has been examined in aqueous tetrahydrofuran. In every instance, ring closure occurred to deliver the syn-2-vinylcyclopentanol exclusively. The corresponding allylsilanes have been prepared as well, and the course of their fluoride ion-induced cyclization was also studied. In these systems, a kinetic bias for formation of the anti-2-vinylcyclopentanol is observed, although not with the same exclusivity. Accordingly, complementarity in product diastereoselectivity can be realized in purposeful fashion. The data acquired in this investigation suggest that the indium-catalyzed reactions involve intramolecularly coordinated transition states where development of a cis 5/6-bicyclic framework is most energetically feasible. In contrast, the silanes appear to utilize open-chain antiperiplanar transition states. While the latter are not particularly sensitive to double-bond geometry, they are responsive to steric compression involving the aryl group.