((1-(cyclopent-1-en-1-yl)vinyl)oxy)triisopropylsilane | 163811-59-4

• 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: ((1-(cyclopent-1-en-1-yl)vinyl)oxy)triisopropylsilane
• 英文别名: 1-triisopropylsiloxy-1-(cyclopenten-1-yl)-ethene；1-(Cyclopenten-1-yl)ethenoxy-tri(propan-2-yl)silane
• CAS: 163811-59-4
• 化学式: C₁₆H₃₀OSi
• 分子量: 266.499
• InChiKey: NIXNFODIINWRKM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  ((1-(cyclopent-1-en-1-yl)vinyl)oxy)triisopropylsilane 在 氢氟酸 作用下， 以 乙腈 为溶剂， 生成 1-乙酰基-1-环戊烯
  参考文献：
  名称：

  Siloxyalkyne–Alkene Metathesis: Rapid Access to Highly Functionalized Enones

  摘要：

  Mechanistically intriguing participation of siloxyalkynes occurs in the intramolecular Ru-catalyzed metathesis with terminal alkenes (see scheme; Ms=methanesulfonyl). Combined with efficient protodesilylation, this process resulted in the development of a new method for the synthesis of highly functionalized enones starting from readily accessible acyclic precursors. Heterocyclic and polycyclic compounds were prepared efficiently, which illustrates the generality of this novel method.

  DOI：

  10.1002/1521-3773(20011119)40:22<4274::aid-anie4274>3.0.co;2-#
• 作为产物：
  描述：

  (hept-6-en-1-ynyloxy)triisopropylsilane 在 [(N,N-(MeSO₂)2-imidazolidin-2-yl)RuCl₂(PCy₃)=CHPh] 作用下， 以 氘代苯 为溶剂， 反应 0.25h， 以98%的产率得到((1-(cyclopent-1-en-1-yl)vinyl)oxy)triisopropylsilane
  参考文献：
  名称：

  Siloxyalkyne–Alkene Metathesis: Rapid Access to Highly Functionalized Enones

  摘要：

  Mechanistically intriguing participation of siloxyalkynes occurs in the intramolecular Ru-catalyzed metathesis with terminal alkenes (see scheme; Ms=methanesulfonyl). Combined with efficient protodesilylation, this process resulted in the development of a new method for the synthesis of highly functionalized enones starting from readily accessible acyclic precursors. Heterocyclic and polycyclic compounds were prepared efficiently, which illustrates the generality of this novel method.

  DOI：

  10.1002/1521-3773(20011119)40:22<4274::aid-anie4274>3.0.co;2-#

文献信息

• A New Approach to the Nazarov Reaction via Sequential Electrocyclic Ring Opening and Ring Closure
  作者：Tina N. Grant、F. G. West

  DOI：10.1021/ja063421a

  日期：2006.7.1

  furnishes vinylcyclopropanol silyl ethers in good yield. Treatment with silver(I) at room temperature effects disrotatory electrocyclic opening to a 2-chloro-3-silyloxypentadienyl cation, which then undergoes conrotatory (Nazarov) electrocyclization to provide chlorocyclopentenones. This two-step sequence offers a convenient and mild alternative to the standard Nazarov cyclization protocol via a formal 4+1

  2-甲硅烷氧基二烯的区域选择性二氯环丙烷化以良好的收率提供乙烯基环丙醇甲硅烷基醚。在室温下用银 (I) 处理会导致旋转电环开环成 2-氯-3-甲硅烷氧基戊二烯基阳离子，然后进行旋转（纳扎罗夫）电环化以提供氯环戊烯酮。这种两步序列通过正式的 4+1 结构为标准 Nazarov 环化方案提供了一种方便且温和的替代方案，并提供含有有用卤素官能团的产品。在一个具有苯基侧基的情况下，观察到生成苯甲茚酮的纳扎罗夫反应中断。
• Reversal of the Regiochemistry in the Rhodium-Catalyzed [4+3] Cycloaddition between Vinyldiazoacetates and Dienes
  作者：Pablo E. Guzmán、Yajing Lian、Huw M. L. Davies

  DOI：10.1002/anie.201406440

  日期：2014.11.24

  regio‐, diastereo‐, and enantioselective [4+3] cycloaddition between vinylcarbenes and dienes has been achieved using the dirhodium tetracarboxylate catalyst [Rh2(S‐BTPCP)4]. This methodology provides facile access to 1,4‐cycloheptadienes that are regioisomers of those formed from the tandem cyclopropanation/Cope rearrangement reaction of vinylcarbenes with dienes.

  使用四羧酸二铑催化剂 [Rh 2 ( S -BTPCP) 4 ]实现了乙烯基卡宾和二烯之间的区域、非对映和对映选择性 [4+3] 环加成反应。这种方法可以轻松获得 1,4-环庚二烯，它们是由乙烯基卡宾与二烯的串联环丙烷化/Cope 重排反应形成的那些的区域异构体。
• Beifuss, Uwe; Gehm, Henning; Noltemeyer, Mathias, Angewandte Chemie, 1995, vol. 107, # 6, p. 705 - 707
  作者：Beifuss, Uwe、Gehm, Henning、Noltemeyer, Mathias、Schmidt, Hans-Georg

  DOI：——

  日期：——
• Siloxyalkyne–Alkene Metathesis: Rapid Access to Highly Functionalized Enones
  作者：Michael P. Schramm、D. Srinivasa Reddy、Sergey A. Kozmin

  DOI：10.1002/1521-3773(20011119)40:22<4274::aid-anie4274>3.0.co;2-#

  日期：2001.11.19

  Mechanistically intriguing participation of siloxyalkynes occurs in the intramolecular Ru-catalyzed metathesis with terminal alkenes (see scheme; Ms=methanesulfonyl). Combined with efficient protodesilylation, this process resulted in the development of a new method for the synthesis of highly functionalized enones starting from readily accessible acyclic precursors. Heterocyclic and polycyclic compounds were prepared efficiently, which illustrates the generality of this novel method.