(-)-[bis-(1R,2S,5R)-(-)-menthyl] 1,3-acetonedicarboxylate | 251565-32-9

• 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-(1R,2S,5R)-(-)-menthyl] 1,3-acetonedicarboxylate
• 英文别名: di-(l)-menthyl 1,3-acetonedicarboxylate；(-)-dimenthyl 1,3-acetonedicarboxylate；bis[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] 3-oxopentanedioate
• CAS: 251565-32-9
• 化学式: C₂₅H₄₂O₅
• 分子量: 422.605
• InChiKey: DYNVMQMUIMOGFG-DTIHPSOBSA-N

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-(1R,2S,5R)-(-)-menthyl] 1,3-acetonedicarboxylate 在 1,3-dimethylimidazolin-3-ium hexafluorophosphate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 (-)-[bis-(1R,2S,5R)-(-)-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 、 L-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95%的产率得到(-)-[bis-(1R,2S,5R)-(-)-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

• Azeotropic Transesterification of β-Keto Esters
  作者：Jens Christoffers、Neclâ Önal

  DOI：10.1002/(sici)1099-0690(200004)2000:8<1633::aid-ejoc1633>3.0.co;2-w

  日期：2000.4

  Transesterifications of methyl β-keto carboxylates catalyzed by DMAP with various high boiling alcohols can be accomplished in refluxing cyclohexane in a Dean-Stark trap. The MeOH formed is removed completely from the reaction mixture as an azeotrope leading to quantitative conversions. The starting materials are converted in stoichiometric ratio, which makes the purification of the product very simple

  由 DMAP 催化的 β-酮羧酸甲酯与各种高沸点醇的酯交换可以在迪安-斯达克分水器中回流环己烷中完成。形成的MeOH作为共沸物从反应混合物中完全去除，导致定量转化。原料以化学计量比进行转化，这使得产物的纯化非常简单并导致高产率。
• Synthesis of (-)-Epibatidine and Its Derivatives from Chiral Allene-1,3-dicarboxylate Esters
  作者：Hiroyuki Kimura、Toshio Fujiwara、Takahiro Katoh、Kiyoharu Nishide、Tetsuya Kajimoto、Manabu Node

  DOI：10.1248/cpb.54.399

  日期：——

  (-)-Epibatidine, an excellent candidate of non-opioidal anesthesia, was formally synthesized in short steps from di-(l)-menthyl (R)-allene-1,3-dicarboxylate that was facilely prepared as a single isomer by means of crystallization-induced asymmetric transformation from a diastereomer mixture of (R)- and (S)-allene-1,3-dicarboxylates. Taking advantage of the chiral synthesis, derivatives of (-)-epibatidine

  （-）-Epibatidine是一种非阿片类药物的极好的候选药物，它是由二-（l）-薄荷基（R）-丙二烯-1,3-二羧酸酯在短时间内正式合成的，方法很简单，即（R）-和（S）-丙二烯-1,3-二羧酸酯的非对映异构体混合物的结晶诱导的不对称转变的机理。利用手性合成的优势，还制备了（-）-表巴替丁衍生物，以靶向可与哺乳动物中枢神经系统中的烟碱乙酰胆碱受体（nAChRs）结合的诊断剂。
• 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。