Methyl endo-7-ethenylbicyclo<4.1.0>heptane-7-carboxylate | 140928-51-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: Methyl endo-7-ethenylbicyclo<4.1.0>heptane-7-carboxylate
• 英文别名: methyl (1R,6R,7R)-7-ethenyl-2-oxabicyclo[4.1.0]heptane-7-carboxylate
• CAS: 140928-51-4
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: LQBLAMHIGFTEMZ-QXFUBDJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl endo-7-ethenylbicyclo<4.1.0>heptane-7-carboxylate 在 氯化二乙基铝 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 以96%的产率得到Methyl (1Hα,6Hα)-5-Oxabicyclo<4.3.0>non-7-ene-7-carboxylate
  参考文献：
  名称：

  Highly stereoselective [3 + 2] annulations by cyclopropanation of vinyl ethers with rhodium(II)-stabilized vinylcarbenoids followed by a formally forbidden 1,3-sigmatropic rearrangement

  摘要：

  A highly stereoselective 3 + 2 annulation has been developed by cyclopropanation of vinyl ethers with rhodium(II)-stabilized vinylcarbenoids to generate vinylcyclopropanes followed by a Et2AlCl-catalyzed 1,3-sigmatropic rearrangement. The success of this methodology rests on the remarkably stereoselectivity that is exhibited in both the cyclopropanation step and also the Et2AlCl-catalyzed vinylcyclopropane rearrangement.

  DOI：

  10.1021/jo00037a041
• 作为产物：
  描述：

  3,4-二氢-2H-吡喃 、 methyl 2-diazobut-3-enoate 在 rhodium(II) octanoate 作用下， 以 正戊烷 为溶剂， 以56%的产率得到Methyl endo-7-ethenylbicyclo<4.1.0>heptane-7-carboxylate
  参考文献：
  名称：

  Highly stereoselective [3 + 2] annulations by cyclopropanation of vinyl ethers with rhodium(II)-stabilized vinylcarbenoids followed by a formally forbidden 1,3-sigmatropic rearrangement

  摘要：

  A highly stereoselective 3 + 2 annulation has been developed by cyclopropanation of vinyl ethers with rhodium(II)-stabilized vinylcarbenoids to generate vinylcyclopropanes followed by a Et2AlCl-catalyzed 1,3-sigmatropic rearrangement. The success of this methodology rests on the remarkably stereoselectivity that is exhibited in both the cyclopropanation step and also the Et2AlCl-catalyzed vinylcyclopropane rearrangement.

  DOI：

  10.1021/jo00037a041

文献信息

• Electrophile-Induced C–C Bond Activation of Vinylcyclopropanes for the Synthesis of <i>Z</i>-Alkylidenetetrahydrofurans
  作者：Venkataraman Ganesh、Taraknath Kundu、Srinivasan Chandrasekaran

  DOI：10.1021/jo302204k

  日期：2013.1.18

  of vinylcyclopropanes as masked donor–acceptor system toward the stereoselective synthesis of Z-alkylidenetetrahydrofurans. Results of bromenium catalyzed indirect activation of C–C bond of vinylcyclopropanes and concomitant cyclization to alkylidenetetrahydrofuran and other heterocycles have been discussed. The stereoselective formation of the Z-isomer is strongly controlled by the extent of destabilization

  我们对乙烯基环丙烷作为掩蔽的供体-受体体系对Z-亚烷基四氢呋喃的立体选择性合成的行为进行了详细研究。讨论了溴催化乙烯基环丙烷的C–C键的间接活化以及伴随环化成亚烷基四氢呋喃和其他杂环的结果。Z的立体选择性形成α-异构体受乙烯基环丙烷的一种薄纱构象异构体的去稳定程度的强烈控制。如在DA环丙烷的情况下，发现开环/环化步骤是立体特异性的。C–C键的活化导致紧密的碳共碳中间体，这从立体化学的完全保留中可以明显看出。构型的保留已通过必要的控制实验确定，该实验排除了双重倒置途径的可能性。目前的结果可作为直接的立体化学证据，以支持紧密的离子对中间体与有争议的S N 2途径。已在B3LYP / 6-31G（d）能级理论上进行了2D势能扫描，以获得构象异构体的相对能量。该ž在构象体的相对种群的基础上，对所观察到的选择性进行了解释，并对在M06–2x / 6-31 + G（d）水平上参与反应的中间和过渡态进行
• Highly stereoselective [3 + 2] annulations by cyclopropanation of vinyl ethers with rhodium(II)-stabilized vinylcarbenoids followed by a formally forbidden 1,3-sigmatropic rearrangement
  作者：Huw M. L. Davies、Baihua Hu

  DOI：10.1021/jo00037a041

  日期：1992.5

  A highly stereoselective 3 + 2 annulation has been developed by cyclopropanation of vinyl ethers with rhodium(II)-stabilized vinylcarbenoids to generate vinylcyclopropanes followed by a Et2AlCl-catalyzed 1,3-sigmatropic rearrangement. The success of this methodology rests on the remarkably stereoselectivity that is exhibited in both the cyclopropanation step and also the Et2AlCl-catalyzed vinylcyclopropane rearrangement.