cis-2-(2-octadiynyl)-3-undecyloxirane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: cis-2-(2-octadiynyl)-3-undecyloxirane
• 英文别名: (+/-)-cis-2-(2,5-Octadiynyl)-3-undecyloxirane；(2R,3S)-2-octa-2,5-diynyl-3-undecyloxirane
• 化学式: C₂₁H₃₄O
• 分子量: 302.5
• InChiKey: KLLWDEKWZYWLTQ-RTWAWAEBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.87
• 重原子数：
  22.0
• 可旋转键数：
  11.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  12.53
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  cis-2-(2-octadiynyl)-3-undecyloxirane 在 Lindlar's catalyst 喹啉 、 氢气 作用下， 以 正戊烷 为溶剂， 反应 1.5h， 以45%的产率得到cis-3,cis-6,cis-9,10-epoxyheneicosadiene
  参考文献：
  名称：

  Alkylative epoxide rearrangement. A stereospecific approach to chiral epoxide pheromones

  摘要：

  The alkylative rearrangement of 1,2-epoxy-3-alkanol tosylates is applied to the synthesis of chiral epoxide pheromones. Attack at the terminal carbon atom of epoxy tosylates by lithioacetylenes and cyclization of the intermediate tosyloxy alcohols produces internal epoxides in high yield. The method is stereospecific: threo-epoxy tosylates give eL's-epoxides, and erythro-epoxy tosylates yield trans-epoxides. Several diastereomerically pure epoxides were prepared in high optical purity from chiral pool intermediates derived from sugars. Pheromone components prepared include (+/-)-cis-epoxyalkene 20 and both enantiomers of cis-epoxy diene 16, a female sex pheromone component of a number of lepidopteran species. These results demonstrate that alkylative rearrangement of 1,2-epoxy-3-alkanol tosylates complements existing methods for stereoselective synthesis of epoxides, including the Payne rearrangement and Sharpless epoxidation.

  DOI：

  10.1021/jo00071a026
• 作为产物：
  描述：

  1-溴十一烷 在 sodium tetrahydroborate 、 正丁基锂 、 乙基溴化镁 、 氢气 、 nickel diacetate 、 lithium 、 乙二胺 、 对甲苯磺酰氯 、 间氯过氧苯甲酸 、 copper(l) chloride 、 lithium chloride 作用下， 以 六甲基磷酰三胺 、 乙醚 、 乙醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 60.0h， 生成 cis-2-(2-octadiynyl)-3-undecyloxirane
  参考文献：
  名称：

  Nikolaeva, L. A.; Kovalev, B. G., Journal of Organic Chemistry USSR (English Translation), 1985, vol. 21, p. 676 - 679

  摘要：

  DOI：

文献信息

• Alkylation epoxide rearrangement. Application to stereoselective synthesis of chiral pheromone epoxides.
  作者：Thomas W. Bell、James A. Ciaccio

  DOI：10.1016/s0040-4039(00)82468-5

  日期：1988.1

  An approach is described for the stereospecific conversion of threo and erythro 1,2-epoxy-3-alkanol tosylates to cis and trans internal epoxides, respectively. The method is illustrated by the synthesis of chiral epoxides, including insect pheromones.

  描述了一种方法，用于将苏式和赤式1,2-环氧-3-链烷醇甲苯磺酸盐的立体定向转化分别为顺式和反式内部环氧化物。通过包括昆虫信息素在内的手性环氧化物的合成说明了该方法。
• BELL, THOMAS W.;CIACCIO, JAMES A., TETRAHEDRON LETT., 29,(1988) N 8, 865-868
  作者：BELL, THOMAS W.、CIACCIO, JAMES A.

  DOI：——

  日期：——
• Nikolaeva, L. A.; Kovalev, B. G., Journal of Organic Chemistry USSR (English Translation), 1985, vol. 21, p. 676 - 679
  作者：Nikolaeva, L. A.、Kovalev, B. G.

  DOI：——

  日期：——
• Alkylative epoxide rearrangement. A stereospecific approach to chiral epoxide pheromones
  作者：Thomas W. Bell、James A. Ciaccio

  DOI：10.1021/jo00071a026

  日期：1993.9

  The alkylative rearrangement of 1,2-epoxy-3-alkanol tosylates is applied to the synthesis of chiral epoxide pheromones. Attack at the terminal carbon atom of epoxy tosylates by lithioacetylenes and cyclization of the intermediate tosyloxy alcohols produces internal epoxides in high yield. The method is stereospecific: threo-epoxy tosylates give eL's-epoxides, and erythro-epoxy tosylates yield trans-epoxides. Several diastereomerically pure epoxides were prepared in high optical purity from chiral pool intermediates derived from sugars. Pheromone components prepared include (+/-)-cis-epoxyalkene 20 and both enantiomers of cis-epoxy diene 16, a female sex pheromone component of a number of lepidopteran species. These results demonstrate that alkylative rearrangement of 1,2-epoxy-3-alkanol tosylates complements existing methods for stereoselective synthesis of epoxides, including the Payne rearrangement and Sharpless epoxidation.