di-(l)-menthyl (S)-allene-1,3-dicarboxylate | 144660-39-9

• 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: di-(l)-menthyl (S)-allene-1,3-dicarboxylate
• 英文别名: (R)-(-)-[bis-(1R,2S,5R)-(-)-menthyl] 2,3-pentadienedioate；(S)-bis-(l)-menthyl 2,3-pentadiendioate；R-di-(-)-menthyl allene-1,3-dicarboxylate
• CAS: 144660-39-9
• 化学式: C₂₅H₄₀O₄
• 分子量: 404.59
• InChiKey: LOYAHPRFQHWQEI-DEYREXOKSA-N

物化性质

• 熔点：
  83 °C(Solv: pentane (109-66-0))
• 沸点：
  482.7±15.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.71
• 重原子数：
  29.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  di-(l)-menthyl (S)-allene-1,3-dicarboxylate 在 三乙胺 作用下， 以 正戊烷 为溶剂， 反应 48.0h， 以90%的产率得到(-)-[bis-(1R,2S,5R)-(-)-menthyl] 2,3-pentadienedioate
  参考文献：
  名称：

  New asymmetric transformation of optically active allene-1,3-dicarboxylate and its application to the formal asymmetric synthesis of (−)-epibatidine

  摘要：

  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。

  DOI：

  10.1039/a806477f
• 作为产物：
  描述：

  (Z)-3-Chloro-pent-2-enedioic acid bis-((1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl) ester 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 生成 di-(l)-menthyl (S)-allene-1,3-dicarboxylate
  参考文献：
  名称：

  光学活性（R）-和（S）-丙二烯-1,3-二羧酸酯的制备及其与环戊二烯的不对称环加成反应

  摘要：

  制备了具有光学活性的（R）-和（S）-丙二烯-1,3-二羧酸酯，并且在路易斯酸存在下它们与环戊二烯的不对称Diels-Alder反应继续以高收率提供了内加合物。

  DOI：

  10.1016/0040-4039(92)89032-8

文献信息

• 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。
• Structure and Asymmetric Diels−Alder Reactions of Optically Active Allene-1,3-dicarboxylates
  作者：Izumi Ikeda、Kazuhiko Honda、Eiji Osawa、Motoo Shiro、Mariko Aso、Ken Kanematsu

  DOI：10.1021/jo951762t

  日期：1996.1.1

  Optically active allene-1,3-dicarboxylates (1a and 2a), which contain the axial asymmetry of the allene moiety, were prepared. The Diels-Alder reaction of 1a and 2a with cyclopentadiene afforded the 1:1 (1a or 2a to cyclopentadiene) endo adducts 3a and 4a through the combination of the sterically favorable approach of the diene and the dienophile owing to the axial asymmetry of the allene moiety and the effective secondary orbital interaction. The absolute configurations of 3a and 4a were determined by chemical transformation and X-ray analysis. The absolute configuration of the axial asymmetry of la was also determined to be R by X-ray analysis.
• A practical improvement of crystallization-induced asymmetric transformation of allene-1,3-dicarboxylates
  作者：Takahiro Katoh、Chie Noguchi、Hiroyuki Kimura、Toshio Fujiwara、Shogo Ichihashi、Kiyoharu Nishide、Tetsuya Kajimoto、Manabu Node

  DOI：10.1016/j.tetasy.2006.11.004

  日期：2006.11

  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.
• Ikeda, Izumi; Gondo, Akie; Shiro, Motoo, Heterocycles, 1993, vol. 36, # 12, p. 2669 - 2672
  作者：Ikeda, Izumi、Gondo, Akie、Shiro, Motoo、Kanematsu, Ken

  DOI：——

  日期：——