diisopropyl(3-methylbut-3-en-1-yn-1-yl)silane | 1569492-45-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: diisopropyl(3-methylbut-3-en-1-yn-1-yl)silane
• 英文别名: 3-Methylbut-3-en-1-ynyl-di(propan-2-yl)silane
• CAS: 1569492-45-0
• 化学式: C₁₁H₂₀Si
• 分子量: 180.365
• InChiKey: MNAOMMGAPVKFBN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.15
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  diisopropyl(3-methylbut-3-en-1-yn-1-yl)silane 在 4-二甲氨基吡啶 、 N-溴代丁二酰亚胺(NBS) 、 三乙胺 作用下， 以 二氯甲烷 、 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  Stabilization, Isomerization and Rearrangement of Enyne [4 + 4]-Cycloadducts

  摘要：

  Reactive 1,2,5-cyclooctatrienes, formed by photocycloaddition of 2-pyridones with enynes, are stabilized by steric shielding, slowing or preventing an otherwise facile [2 + 2]-dimerization reaction. Diisopropylsilyl ether-tethered reactants paired with an alkene substituent (R) produce allenes that are stable (R = TMS) or that isomerize to 1,3-dienes by hydrogen migration (R = alkyl). Under acidic conditions, hydrolysis of the photoproduct's silyl ether can lead to a [3,3]-sigmatropic rearrangement.

  DOI：

  10.1021/ol501831a
• 作为产物：
  描述：

  二异丙基氯代硅烷 、 2-甲基-1-丁烯-3-炔 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以100%的产率得到diisopropyl(3-methylbut-3-en-1-yn-1-yl)silane
  参考文献：
  名称：

  Stabilization, Isomerization and Rearrangement of Enyne [4 + 4]-Cycloadducts

  摘要：

  Reactive 1,2,5-cyclooctatrienes, formed by photocycloaddition of 2-pyridones with enynes, are stabilized by steric shielding, slowing or preventing an otherwise facile [2 + 2]-dimerization reaction. Diisopropylsilyl ether-tethered reactants paired with an alkene substituent (R) produce allenes that are stable (R = TMS) or that isomerize to 1,3-dienes by hydrogen migration (R = alkyl). Under acidic conditions, hydrolysis of the photoproduct's silyl ether can lead to a [3,3]-sigmatropic rearrangement.

  DOI：

  10.1021/ol501831a

文献信息

• Syntheses of 2-silicon-substituted 1,3-dienes
  作者：Partha P. Choudhury、Christopher S. Junker、Ramakrishna R. Pidaparthi、Mark E. Welker

  DOI：10.1016/j.jorganchem.2013.12.046

  日期：2014.3

  A number of 2-silicon substituted 1,3-dienes have been prepared by one of three routes: 1) Reactions of 1,3-dienyl Grignard reagents with silyl electrophiles or silyl Grignard reagents with 1,3-dienyl electrophiles; 2) Hydrosilylation of enynes; 3) Enyne cross metathesis. The strengths and limitations of each preparative method are discussed. (C) 2013 Elsevier B. V. All rights reserved.
• Enyne-2-pyrone [4 + 4]-Photocycloaddition: Sesquiterpene Synthesis and a Low-Temperature Cope Rearrangement
  作者：Buddha B. Khatri、Scott McN. Sieburth

  DOI：10.1021/acs.orglett.5b02207

  日期：2015.9.4

  Intramolecular [4 + 4] photoreaction of 2-pyrones with a 1,3-enyne yields an unstable 1,2,5-cyclooctatriene product. Without a C4 pyrone substituent, 1,3-hydrogen migration converts the allene to a 1,3-diene, with a skeleton related to dactylol. With methoxy substitution, Cope rearrangement yields a nine-membered ring fused to a cyclobutane. Both structures were confirmed by X-ray crystallography. The Cope rearrangement is apparently reversible, reforming the allene which undergoes a proton shift to the more stable 1,3-diene product.