1,1-di-(-)-menthyl 2-methyl ethene-1,1,2-tricarboxylate | 223693-84-3

• 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 2-methyl ethene-1,1,2-tricarboxylate
• 英文别名: 2-O-methyl 1-O,1-O-bis[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] ethene-1,1,2-tricarboxylate
• CAS: 223693-84-3
• 化学式: C₂₆H₄₂O₆
• 分子量: 450.616
• InChiKey: BFXMJYLWCFASQG-WTGUXPOUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.2
• 重原子数：
  32
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-(phenylseleno)-2-(trimethylsilyl)ethene 、 1,1-di-(-)-menthyl 2-methyl ethene-1,1,2-tricarboxylate 在 zinc dibromide 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 2-((1R,2S,5R)-2-Isopropyl-5-methyl-cyclohexyloxycarbonyl)-3-((Z)-2-phenylselanyl-vinyl)-succinic acid 1-((1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl) ester 4-methyl ester 、 2-((1R,2S,5R)-2-Isopropyl-5-methyl-cyclohexyloxycarbonyl)-3-((E)-2-phenylselanyl-vinyl)-succinic acid 1-((1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl) ester 4-methyl 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：

  1,1-di-(-)-menthyl 2-methylethane-1,1,2-tricarboxylate 在 偶氮二异丁腈 、 溴 、 三乙胺 作用下， 以 四氯化碳 、 乙醚 为溶剂， 反应 32.0h， 生成 1,1-di-(-)-menthyl 2-methyl ethene-1,1,2-tricarboxylate
  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.