Ethyl 5-methylhex-4-EN-2-ynoate | 921882-58-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Ethyl 5-methylhex-4-EN-2-ynoate
• 英文别名: ethyl 5-methylhex-4-en-2-ynoate
• CAS: 921882-58-8
• 化学式: C₉H₁₂O₂
• 分子量: 152.193
• InChiKey: UOFXQKRNMBLQTD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.44
• 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：

  Ethyl 5-methylhex-4-EN-2-ynoate 、 1,1-Dimethyl-2,4-bis(trimethylsilyloxy)-cyclohexa-3,4-diene 反应 24.0h， 生成 Ethyl 2,4-dihydroxy-6-(2-methylprop-1-en-1-yl)benzoate 、 Ethyl 3,5-dihydroxy-2-(2-methylprop-1-en-1-yl)benzoate
  参考文献：
  名称：

  Highly Selective Diels-Alder Reactions of Directly Connected Enyne Dienophiles

  摘要：

  The paper describes the course of cycloadditions of Diels-Alder dienophiles containing linked enyne sites, each substituted with activating groups. Consistently, it was found that in the enyne cases the Diels-Alder reaction occurred specifically at the acetylenic center. Furthermore, it was found that the regiochemical sense of the cycloaddition was apparently determined by the remote activating group bound to the olefinic site. This remote acrylyl group totally dominated the course of the cycloaddition, relative to the activating group bound directly on the acetylene site. Explanations for these findings at the computational level are provided. The computations also rationalize the strong preference for cycloaddition to occur at the acetylene linkage and encompass the otherwise surprising regiochemical dominance by the remote ester on the olefinic site. The high selectivities available through such reactions provide important new opportunities in the synthesis of orsenillate type substructures that are found in a variety of natural products of contemporary interest.

  DOI：

  10.1021/ja065762u

文献信息

• Highly Selective Diels-Alder Reactions of Directly Connected Enyne Dienophiles
  作者：Mingji Dai、David Sarlah、Maolin Yu、Samuel J. Danishefsky、Gavin O. Jones、K. N. Houk

  DOI：10.1021/ja065762u

  日期：2007.1.1

  The paper describes the course of cycloadditions of Diels-Alder dienophiles containing linked enyne sites, each substituted with activating groups. Consistently, it was found that in the enyne cases the Diels-Alder reaction occurred specifically at the acetylenic center. Furthermore, it was found that the regiochemical sense of the cycloaddition was apparently determined by the remote activating group bound to the olefinic site. This remote acrylyl group totally dominated the course of the cycloaddition, relative to the activating group bound directly on the acetylene site. Explanations for these findings at the computational level are provided. The computations also rationalize the strong preference for cycloaddition to occur at the acetylene linkage and encompass the otherwise surprising regiochemical dominance by the remote ester on the olefinic site. The high selectivities available through such reactions provide important new opportunities in the synthesis of orsenillate type substructures that are found in a variety of natural products of contemporary interest.