(+)-[bis-(1S,2R,5S)-(+)-menthyl] 1,3-acetonedicarboxylate | 922148-90-1

• 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: (+)-[bis-(1S,2R,5S)-(+)-menthyl] 1,3-acetonedicarboxylate
• 英文别名: bis[(1S,2R,5S)-5-methyl-2-propan-2-ylcyclohexyl] 3-oxopentanedioate
• CAS: 922148-90-1
• 化学式: C₂₅H₄₂O₅
• 分子量: 422.605
• InChiKey: DYNVMQMUIMOGFG-FMIOCKMGSA-N

物化性质

• 沸点：
  486.9±20.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  30
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  (+)-[bis-(1S,2R,5S)-(+)-menthyl] 1,3-acetonedicarboxylate 在 1,3-dimethylimidazolin-3-ium hexafluorophosphate 、 三乙胺 作用下， 反应 1.5h， 生成 [bis-(1S,2R,5S)-(+)-menthyl] 2,3-pentadienedioate
  参考文献：
  名称：

  A practical improvement of crystallization-induced asymmetric transformation of allene-1,3-dicarboxylates

  摘要：

  Enantiomerically pure allene-1,3-dicarboxylates were easily synthesized by using epimerization-crystallization of dissymmetric allene compounds, which were prepared from acetone-1,3-dicarboxylates and naturally abundant chiral alcohols, that is, (-)and (+)-menthols, borneol, and isoborneol. After scrutinizing the crystallization of several allene-1,3-dicarboxylates in the presence of triethylamine, it was found that allene-1,3-dicarboxylate carrying bornyl groups was the most easily prepared as a single isomer because of it having suitable solubility to be crystallized in hexane at 0 degrees C to room temperature. Diels-Alder reaction of the enantiomerically pure allene-1,3-dicarboxylates and cyclic dienes, such as N-Boc-pyrrole and cyclopentadiene, afforded endo-adducts having the same configurations at two newly generated stereogenic centers. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.11.004
• 作为产物：
  描述：

  1,3-丙酮二羧酸二甲酯 、 D-薄荷醇 在 4-二甲氨基吡啶 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以72%的产率得到(+)-[bis-(1S,2R,5S)-(+)-menthyl] 1,3-acetonedicarboxylate
  参考文献：
  名称：

  A practical improvement of crystallization-induced asymmetric transformation of allene-1,3-dicarboxylates

  摘要：

  Enantiomerically pure allene-1,3-dicarboxylates were easily synthesized by using epimerization-crystallization of dissymmetric allene compounds, which were prepared from acetone-1,3-dicarboxylates and naturally abundant chiral alcohols, that is, (-)and (+)-menthols, borneol, and isoborneol. After scrutinizing the crystallization of several allene-1,3-dicarboxylates in the presence of triethylamine, it was found that allene-1,3-dicarboxylate carrying bornyl groups was the most easily prepared as a single isomer because of it having suitable solubility to be crystallized in hexane at 0 degrees C to room temperature. Diels-Alder reaction of the enantiomerically pure allene-1,3-dicarboxylates and cyclic dienes, such as N-Boc-pyrrole and cyclopentadiene, afforded endo-adducts having the same configurations at two newly generated stereogenic centers. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.11.004

文献信息

• New asymmetric transformation of optically active allene-1,3-dicarboxylate and its application to the formal asymmetric synthesis of (−)-epibatidine
  作者：Manabu Node、Kiyoharu Nishide、Toshio Fujiwara、Shogo Ichihashi

  DOI：10.1039/a806477f

  日期：——

  A new efficient synthesis of di-(–)-L-menthyl (R)-allene-1,3-dicarboxylate [(R)-1] involving asymmetric transformation through epimerization–crystallization with the assistance of a catalytic amount of Et3N was developed; the highly endo-selective asymmetric Diels–Alder reaction of (R)-1 with N-Boc-pyrrole for the asymmetric synthesis of 7-tert-butoxycarbonyl-7-azabicyclo[2.2.1]heptan-2-one [(–)-6], a synthetic intermediate of (–)-epibatidine, is described.

  一种新的高效合成二-(α)-L-薄荷基(R)-丙二烯-1,3-二羧酸酯[(R)-1]的方法，涉及在催化量的辅助下通过差向异构化-结晶的不对称转化Et3N被开发出来； (R)-1 与 N-Boc-吡咯的高度内选择性不对称 DielsâAlder 反应，用于不对称合成 7-叔丁氧基羰基-7-氮杂双环[2.2.1]庚烷-2-酮 [(â描述了(R)-6]，一种(R)-Epibatidine 的合成中间体。