1,1-di-(-)-menthyl oxomalonate | 155306-00-6

• 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: 1,1-di-(-)-menthyl oxomalonate
• 英文别名: bis[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] 2-oxopropanedioate
• CAS: 155306-00-6
• 化学式: C₂₃H₃₈O₅
• 分子量: 394.552
• InChiKey: KIPUPVFYELVPGG-XRNRSJMDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.2
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,1-di-(-)-menthyl oxomalonate 在 zinc dibromide 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 7.0h， 生成 2-(3-Phenyl-propionyl)-3-(phenylselanyl-trimethylsilanyl-methyl)-cyclopropane-1,1-dicarboxylic acid bis-((1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl) ester
  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：

  bis((1S,2R,5S)-2-isopropyl-5-methylcyclohexyl) 2-benzylidenemalonate 在 臭氧 作用下， 以 二氯甲烷 为溶剂， 反应 31.5h， 生成 1,1-di-(-)-menthyl oxomalonate
  参考文献：
  名称：

  DIALKYL MESOXALATES BY OZONOLYSIS OF DIALKYL BENZALMALONATES: DIMETHYL MESOXALATE

  摘要：

  DOI：

  10.15227/orgsyn.071.0214

文献信息

• Synthesis of Vicinal Trioxo Compounds by Dimethyl Dioxirane Oxidation of 2-Diazo-1,3-dioxo Derivatives
  作者：A. Saba

  DOI：10.1080/00397919408012648

  日期：1994.3

  A convenient preparation of vicinal triketones, alpha, beta-dioxoesters and 2-oxomalonates is described.
• 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.
• DIALKYL MESOXALATES BY OZONOLYSIS OF DIALKYL BENZALMALONATES: DIMETHYL MESOXALATE
  作者：Tietze, Lutz F.、Bratz, Matthias

  DOI：10.15227/orgsyn.071.0214

  日期：——