diethyl (2-oxohex-5-enyl)phosphonate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl (2-oxohex-5-enyl)phosphonate
• 英文别名: diethyl (2-oxohex-5-en-1-yl)phosphonate；(2-oxo-hex-5-enyl)-phosphonic acid diethyl ester；1-Diethoxyphosphorylhex-5-en-2-one
• 化学式: C₁₀H₁₉O₄P
• 分子量: 234.232
• InChiKey: HRPLGKHQRBIGKW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  15
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl (2-oxohex-5-enyl)phosphonate 、 丙烯酸乙酯 在 phosphine-free Hoveyda-Grubbs catalyst 作用下， 以 二氯甲烷 为溶剂， 100.0 ℃ 、450.0 kPa 条件下， 反应 0.25h， 以81%的产率得到ethyl 7-(diethoxyphosphoryl)-6-oxohept-2-enoate
  参考文献：
  名称：

  Cross-Metathesis Assisted by Microwave Irradiation

  摘要：

  [GRAPHICS]Microwave irradiation effectively accelerates cross-coupling metathesis reactions between deactivated olefins. Reactions have been carried out with the phosphine-free Hoveyda-Grubbs catalyst and the "second generation Grubbs' catalyst." While there have been reports that a "microwave effect" is observed in various transformations, the accelerations we observe are due to the efficient and rapid heating and increased pressure in the microwave apparatus.

  DOI：

  10.1021/jo0514624
• 作为产物：
  描述：

  丙酮基膦酸二乙酯 、 丙烯酰碘 在 sodium hydride 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 5.0h， 以75%的产率得到diethyl (2-oxohex-5-enyl)phosphonate
  参考文献：
  名称：

  Cross-Metathesis Assisted by Microwave Irradiation

  摘要：

  [GRAPHICS]Microwave irradiation effectively accelerates cross-coupling metathesis reactions between deactivated olefins. Reactions have been carried out with the phosphine-free Hoveyda-Grubbs catalyst and the "second generation Grubbs' catalyst." While there have been reports that a "microwave effect" is observed in various transformations, the accelerations we observe are due to the efficient and rapid heating and increased pressure in the microwave apparatus.

  DOI：

  10.1021/jo0514624

文献信息

• Organocatalytic Enantioselective Vinylcyclopropane‐Cyclopentene (VCP‐CP) Rearrangement
  作者：Gorka Garay、Josebe Hurtado、Manuel Pedrón、Lorena García、Efraim Reyes、Eduardo Sánchez‐Díez、Tomás Tejero、Luisa Carrillo、Pedro Merino、Jose L. Vicario

  DOI：10.1002/anie.202302416

  日期：2023.5.22

  2-Alkenyl-substituted cyclopropylacetaldehydes undergo enantioselective vinylcyclopropane-cyclopentene (VCP-CP) rearrangement using a Jorgensen-Hayashi-type catalyst. The reaction proceeds through enamine/iminium activation and comprises the in situ generation of a donor-acceptor cyclopropane intermediate that undergoes ring-opening/cyclization. Computational studies together with the experimental

  2-烯基取代的环丙基乙醛使用 Jorgensen-Hayashi 型催化剂进行对映选择性乙烯基环丙烷-环戊烯 (VCP-CP) 重排。该反应通过烯胺/亚胺活化进行，包括原位生成供体-受体环丙烷中间体，该中间体经历开环/环化。计算研究连​​同实验数据支持 II 型 DYKAT 过程运行。