di-(-)-menthyl 2-vinylcyclopropane-1,1-dicarboxylate | 84646-69-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: di-(-)-menthyl 2-vinylcyclopropane-1,1-dicarboxylate
• 英文别名: bis[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] (2R)-2-ethenylcyclopropane-1,1-dicarboxylate
• CAS: 84646-69-5
• 化学式: C₂₇H₄₄O₄
• 分子量: 432.644
• InChiKey: VIKYKZUDNSFCNE-USVXRKKKSA-N

物化性质

• 沸点：
  469.1±45.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  31
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.85
• 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：

  di-(-)-menthyl 2-vinylcyclopropane-1,1-dicarboxylate 在 sodium hydroxide 、 水 、 对苯二酚 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 8.0h， 生成 (R)-2-Vinyl-1,1-cyclopropandicarbonsaeure-dimethylester
  参考文献：
  名称：

  Chiral Synthesis of Cyclopropanes. Stereoselective [2 + 1] Cycloaddition Reactions of 1-Seleno-2-silylethenes with Di-(−)-menthyl Ethene-1,1-dicarboxylates

  摘要：

  Reaction of 1-seleno-2-silylethenes 1 with the chiral electrophiles 2, 3, and 4 derived from (-)menthol, in the presence of zinc halides gave the cyclopropane products 5, 6, and 7, respectively, with high diastereoselectivity. The absolute configuration of 5a, prepared by the reaction of 1-(phenylseleno)-2-(trimethylsilyl)ethene (la) and di-(-)-menthyl methylenemalonate (2), was determined to be 2S by conversion to the known chiral compound 11. The proposed mechanism, involving fixation of the (-)-menthyl group to the C=C plane by the Lewis acid in the addition step, is consistent with the experimental observations. A selenium-participating secondary orbital interaction in the synclinal addition path was elucidated by ab initio calculations and explained the observed diasteroselectivity.

  DOI：

  10.1021/jo9820925
• 作为产物：
  描述：

  di-(-)-menthyl methylenemalonate 在 sodium periodate 、 正丁基锂 、 dimenthyl malonate 、 zinc(II) iodide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 10.5h， 生成 di-(-)-menthyl 2-vinylcyclopropane-1,1-dicarboxylate
  参考文献：
  名称：

  Chiral Synthesis of Cyclopropanes. Stereoselective [2 + 1] Cycloaddition Reactions of 1-Seleno-2-silylethenes with Di-(−)-menthyl Ethene-1,1-dicarboxylates

  摘要：

  Reaction of 1-seleno-2-silylethenes 1 with the chiral electrophiles 2, 3, and 4 derived from (-)menthol, in the presence of zinc halides gave the cyclopropane products 5, 6, and 7, respectively, with high diastereoselectivity. The absolute configuration of 5a, prepared by the reaction of 1-(phenylseleno)-2-(trimethylsilyl)ethene (la) and di-(-)-menthyl methylenemalonate (2), was determined to be 2S by conversion to the known chiral compound 11. The proposed mechanism, involving fixation of the (-)-menthyl group to the C=C plane by the Lewis acid in the addition step, is consistent with the experimental observations. A selenium-participating secondary orbital interaction in the synclinal addition path was elucidated by ab initio calculations and explained the observed diasteroselectivity.

  DOI：

  10.1021/jo9820925

文献信息

• Chiral Synthesis of Cyclopropanes. Stereoselective [2 + 1] Cycloaddition Reactions of 1-Seleno-2-silylethenes with Di-(−)-menthyl Ethene-1,1-dicarboxylates
  作者：Shoko Yamazaki、Hitomi Kataoka、Shinichi Yamabe

  DOI：10.1021/jo9820925

  日期：1999.4.1

  Reaction of 1-seleno-2-silylethenes 1 with the chiral electrophiles 2, 3, and 4 derived from (-)menthol, in the presence of zinc halides gave the cyclopropane products 5, 6, and 7, respectively, with high diastereoselectivity. The absolute configuration of 5a, prepared by the reaction of 1-(phenylseleno)-2-(trimethylsilyl)ethene (la) and di-(-)-menthyl methylenemalonate (2), was determined to be 2S by conversion to the known chiral compound 11. The proposed mechanism, involving fixation of the (-)-menthyl group to the C=C plane by the Lewis acid in the addition step, is consistent with the experimental observations. A selenium-participating secondary orbital interaction in the synclinal addition path was elucidated by ab initio calculations and explained the observed diasteroselectivity.