2-(pent-4-enyloxy)-2-vinyl-cyclopentanone | 890903-63-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(pent-4-enyloxy)-2-vinyl-cyclopentanone
• 英文别名: (2R)-2-ethenyl-2-pent-4-enoxycyclopentan-1-one
• CAS: 890903-63-6
• 化学式: C₁₂H₁₈O₂
• 分子量: 194.274
• InChiKey: LKCITOWRBRZJJN-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(pent-4-enyloxy)-2-vinyl-cyclopentanone 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 作用下， 以 二氯甲烷 为溶剂， 以100%的产率得到6-oxa-spiro[4.5]dec-9-en-1-one
  参考文献：
  名称：

  Palladium-Catalyzed Diastereo- and Enantioselective Wagner−Meerwein Shift: Control of Absolute Stereochemistry in the C−C Bond Migration Event

  摘要：

  Inducing absolute stereochemistry in Wagner-Meerwein shifts was examined in a ring expansion protocol. Initiated by generation of a pi-allylpalladium intermediate by hydropalladation of allenes, the ring expansion of allenylcyclobutanol substrates proceeded with excellent diastereo- and enantioselectivities. The results demonstrate that, during the C-C bond migration process, our chiral catalysts can control the stereochemistry of both the pi-allylpalladium intermediate and the corresponding migration bond. Moreover, the stereochemical outcome of the reaction can be rationalized very well with the working model of the chiral catalyst. The method provides an efficient way to synthesize highly substituted cyclopentanones with an alpha-chiral O-tertiary center which has various synthetic applications.

  DOI：

  10.1021/ja7111299
• 作为产物：
  描述：

  1-(1-pent-4-enyloxy-propa-1,2-dienyl)-cyclobutanol 在 (dibenzylideneacetone)3palladium⁽⁰⁾ monochloroform complex 、 (R,R)-stilbene ligand 4 A molecular sieve 、 三乙胺 、 苯甲酸 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 12.0h， 生成 2-(pent-4-enyloxy)-2-vinyl-cyclopentanone 、 2-(pent-4-enyloxy)-2-vinyl-cyclopentanone
  参考文献：
  名称：

  Palladium-Catalyzed Diastereo- and Enantioselective Wagner−Meerwein Shift: Control of Absolute Stereochemistry in the C−C Bond Migration Event

  摘要：

  Inducing absolute stereochemistry in Wagner-Meerwein shifts was examined in a ring expansion protocol. Initiated by generation of a pi-allylpalladium intermediate by hydropalladation of allenes, the ring expansion of allenylcyclobutanol substrates proceeded with excellent diastereo- and enantioselectivities. The results demonstrate that, during the C-C bond migration process, our chiral catalysts can control the stereochemistry of both the pi-allylpalladium intermediate and the corresponding migration bond. Moreover, the stereochemical outcome of the reaction can be rationalized very well with the working model of the chiral catalyst. The method provides an efficient way to synthesize highly substituted cyclopentanones with an alpha-chiral O-tertiary center which has various synthetic applications.

  DOI：

  10.1021/ja7111299

文献信息

• Palladium-Catalyzed Diastereo- and Enantioselective Wagner−Meerwein Shift: Control of Absolute Stereochemistry in the C−C Bond Migration Event
  作者：Barry M. Trost、Jia Xie

  DOI：10.1021/ja7111299

  日期：2008.5.1

  Inducing absolute stereochemistry in Wagner-Meerwein shifts was examined in a ring expansion protocol. Initiated by generation of a pi-allylpalladium intermediate by hydropalladation of allenes, the ring expansion of allenylcyclobutanol substrates proceeded with excellent diastereo- and enantioselectivities. The results demonstrate that, during the C-C bond migration process, our chiral catalysts can control the stereochemistry of both the pi-allylpalladium intermediate and the corresponding migration bond. Moreover, the stereochemical outcome of the reaction can be rationalized very well with the working model of the chiral catalyst. The method provides an efficient way to synthesize highly substituted cyclopentanones with an alpha-chiral O-tertiary center which has various synthetic applications.