(3-(but-3-enyl)cyclopent-1-enyloxy)trimethylsilane | 130741-35-4

• 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: (3-(but-3-enyl)cyclopent-1-enyloxy)trimethylsilane
• 英文别名: (3-But-3-enylcyclopenten-1-yl)oxy-trimethylsilane
• CAS: 130741-35-4
• 化学式: C₁₂H₂₂OSi
• 分子量: 210.392
• InChiKey: SYUUTXOTUGAENT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (3-(but-3-enyl)cyclopent-1-enyloxy)trimethylsilane 在 9,10-二氰基蒽 作用下， 以 乙腈 为溶剂， 反应 113.0h， 以11%的产率得到cis-octahydro-1H-inden-1-one
  参考文献：
  名称：

  通过光诱导电子转移对不饱和甲硅烷基烯醇醚进行区域和立体选择性环化反应——机理方面和合成方法

  摘要：

  氧化光诱导电子转移 (PET) 反应已经用各种带有烯属或甲硅烷基炔属侧链的甲硅烷基烯醇醚和甲硅烷氧基-2H-色酮进行，反应导致区域选择性闭环，形成具有孔的双环至四环系统-定义的环接点，例如全氢菲酮 13 或苯并退火的呫吨酮 24。我们的研究集中在该环化方法在辐照时间和产品产率方面的优化。使用共敏化 PET 方法可以减少辐照时间。在甲硅烷基上修饰底物可提高产率。此外，我们发现溶剂和压力依赖性是重要的工具，可以控制区域化学。实现了通过自由基阳离子反应途径合成 6-endo 产物，以及通过自由基中间体实现 5-exo 闭环。讨论了机械细节，包括氘标记实验的发现。

  DOI：

  10.1002/(sici)1099-0690(199808)1998:8<1583::aid-ejoc1583>3.0.co;2-r
• 作为产物：
  描述：

  三甲基氯硅烷 、 2-环戊烯酮 、 3-Butenylmagnesium bromide 在 六甲基磷酰三胺 、 copper(I) bromide dimethylsulfide complex 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 (3-(but-3-enyl)cyclopent-1-enyloxy)trimethylsilane
  参考文献：
  名称：

  双环[4.3.0]壬烷，双环[3.3.0]辛烷及相关的苯并衍生物的简单构建方法是通过钯催化的环烯基化反应。

  摘要：

  [反应：见正文]双环[4.3.0]壬烷（氢化丙烷）和双环[3.3.0]辛烷（八氢戊烯）很容易通过钯催化的环烯基化反应合成。另外，在乙酸钯催化作用下，通过甲硅烷基烯醇醚与芳环之间的分子内偶联，首次制备了苯并稠合的双环[3.3.0]辛烷。

  DOI：

  10.1021/ol020187u

文献信息

• Iron(<scp>III</scp>) mediated transformations of cyclopropyltrimethylsilyl ethers. Part 1. Free radical tandem ring expansion–cyclisation reactions for the rapid construction of [n.3.0] bicyclic ring systems
  作者：Kevin I. Booker-Milburn、David F. Thompson

  DOI：10.1039/p19950002315

  日期：——

  trimethylsilyl ethers with anhydrous ferric chloride in dry dimethylformamide leads to diastereoisomerically pure [n.3.0] bicyclic chloro ketones by a novel tandem ring expansion–cyclisation sequence. The reaction is thought to proceed by a mechanism involving the intermediacy of a cyclopropyl alkoxy radical.

  在干燥的二甲基甲酰胺中用无水氯化铁处理许多[ n .1.0]环丙基三甲基甲硅烷基醚会导致新的串联环扩环序列，从而形成非对映异构纯的[ n .3.0]双环氯酮。该反应被认为是通过涉及环丙基烷氧基的中间体的机理来进行的。
• Studies towards the Synthesis of Pentalenene: Mechanistic Insights into the Isomerization Phenomenon During RCM of Medium-Sized Rings
  作者：Guillaume De Bo、István E. Markó

  DOI：10.1002/ejoc.201001475

  日期：2011.4

  Isomerization issues have been encountered during the ring-closing metathesis (RCM) step of a new approach towards pentalenene. This paper describes the mechanistic insights gained during the study of this side reaction from a substrate perspective. Isomerization issues have been encountered during the RCM step of a new approach towards pentalenene.

  在戊烯新方法的闭环复分解 (RCM) 步骤中遇到了异构化问题。本文从底物的角度描述了在研究这种副反应期间获得的机理见解。在对戊烯的新方法的 RCM 步骤中遇到了异构化问题。
• Intramolecular radical cyclization of silylacetylenic or olefinic α-iodo ketones: Application to the total synthesis of (±)-modhephene
  作者：Sha Chin-Kang、Jean Tsong-Shin、Wang Deh-Chi

  DOI：10.1016/s0040-4039(00)97460-4

  日期：——

  Silylacetylenic or olefinic α-iodo ketones were treated with tributyltin hydride and AIBN to give bicyclic ketones by an intramolecular α-carbonyl radical cyclization reaction. As an application of this radical cyclization reaction, the total synthesis of (±)-modhephene has been accomplished efficiently.

  用氢化三丁基锡和AIBN处理甲硅烷基或烯属α-碘酮，通过分子内α-羰基自由基环化反应得到双环酮。作为该自由基环化反应的一种应用，已经有效地完成了（±）-二苯乙烯的全合成。
• A facile synthesis of bicyclo[m.n.1]alkan-1-ols. Evidence for organosamarium intermediates in the samarium(II) iodide promoted intramolecular Barbier-type reaction
  作者：Gary A. Molander、Jeffrey A. McKie

  DOI：10.1021/jo00013a008

  日期：1991.6

  Samarium(II) iodide (SmI2) has been successfully employed as a reductive coupling agent for the intramolecular Barbier-type synthesis of bicyclo[m.n.1]alkan-1-ols. Thus, a variety of 3-(omega-iodoalkyl)cycloalkanones, upon treatment with SmI2 and a catalytic quantity of iron complex in tetrahydrofuran (THF), provide the title compounds in excellent yields. The reaction is quite general for the construction of diverse bicyclic ring systems, including the highly strained bicyclo[2.1.1]hexan-1-ol. In addition to exploring the synthetic utility of this reaction, studies have been performed which provide insight on the mechanistic details of the SmI2-promoted intramolecular Barbier-type synthesis. Compelling evidence for the intermediacy of organosamarium species has thus been gathered.
• A new 4-substituted-2-Cyclohexenone synthesis
  作者：Kevin I. Booker-Milburn、David F. Thompson

  DOI：10.1016/s0040-4039(00)79311-7

  日期：1993.11

  Conjugate addition of a variety of Grignard reagents to 2-cyclopentenone followed by cyclopropanation of the resulting enol ethers gave a range of substituted cyclopropyl silyl ethers in good yield. Treatment of these cyclopropyl silyl ethers with ferric chloride in DMF gave the one carbon ring expanded beta-chloro ketones which were eliminated to the corresponding 4- substituted-2-cyclohexenones.