(S)-1-(Tetrahydropyranyloxy)-10-methyltridec-1-ene

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (S)-1-(Tetrahydropyranyloxy)-10-methyltridec-1-ene
• 英文别名: 2-[(10S)-10-methyltridec-12-enoxy]oxane
• 化学式: C₁₉H₃₆O₂
• 分子量: 296.494
• InChiKey: ARCNLSOSNHGWST-MRTLOADZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  21
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-1-(Tetrahydropyranyloxy)-10-methyltridec-1-ene 在 4-甲基苯磺酸吡啶 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以96%的产率得到(S)-10-Methyl-tridec-12-en-1-ol
  参考文献：
  名称：

  Preparation of the versatile chiron, (R)- and (S)-12-(tetrahydropyranyloxy)-3-methyldodecan-1-ol: application to the syntheses of methyl branched insect pheromones

  摘要：

  A convenient chemoenzymatic synthesis for the title methyl branched chiron has been developed starting from 10-undecenoic acid (1). Thus, 1 was converted to 1-(tetrahydropyranyloxy)-10-undecan-2-one (4) which on reaction with triethyl phosphonoacetate and subsequent functionalization led to the racemic chiron 7. This was resolved via C. rugosa lipase-catalyzed acetylation and subsequently used for the syntheses of some chiral insect pheromones. Thus, (S)-7 was mesylated, reduced with LAH and acetylated to give the pheromone (R)-10-methyldodecan-1-yl acetate (I), while its oxidation to the aldehyde 10 followed by Wittig reaction with methylenephosphorane, depyranylation, and hydrogenation gave the alcohol 12. Its tosylation, detosylation, and Hg2+-catalyzed hydration furnished (R)-10-methyltridecan-2-one (II). Likewise, Wittig reaction of (R)-10 with a suitable phosphorane and similar protocol as above afforded the alcohol 14. Its tosylate was coupled with 3-butenylmagnesium bromide to furnish pheromone (S)-14-methyloctadecene (III).

  DOI：

  10.1021/jo00118a047
• 作为产物：
  描述：

  甲基三苯基碘化鏻 、 (S)-12-(Tetrahydropyranyloxy)-3-methyldodecanal 在 dimethyl sulfoxide; deprotonated form 作用下， 以84%的产率得到(S)-1-(Tetrahydropyranyloxy)-10-methyltridec-1-ene
  参考文献：
  名称：

  Preparation of the versatile chiron, (R)- and (S)-12-(tetrahydropyranyloxy)-3-methyldodecan-1-ol: application to the syntheses of methyl branched insect pheromones

  摘要：

  A convenient chemoenzymatic synthesis for the title methyl branched chiron has been developed starting from 10-undecenoic acid (1). Thus, 1 was converted to 1-(tetrahydropyranyloxy)-10-undecan-2-one (4) which on reaction with triethyl phosphonoacetate and subsequent functionalization led to the racemic chiron 7. This was resolved via C. rugosa lipase-catalyzed acetylation and subsequently used for the syntheses of some chiral insect pheromones. Thus, (S)-7 was mesylated, reduced with LAH and acetylated to give the pheromone (R)-10-methyldodecan-1-yl acetate (I), while its oxidation to the aldehyde 10 followed by Wittig reaction with methylenephosphorane, depyranylation, and hydrogenation gave the alcohol 12. Its tosylation, detosylation, and Hg2+-catalyzed hydration furnished (R)-10-methyltridecan-2-one (II). Likewise, Wittig reaction of (R)-10 with a suitable phosphorane and similar protocol as above afforded the alcohol 14. Its tosylate was coupled with 3-butenylmagnesium bromide to furnish pheromone (S)-14-methyloctadecene (III).

  DOI：

  10.1021/jo00118a047

文献信息

• Preparation of the versatile chiron, (R)- and (S)-12-(tetrahydropyranyloxy)-3-methyldodecan-1-ol: application to the syntheses of methyl branched insect pheromones
  作者：S. Sankaranarayanan、A. Sharma、B. A. Kulkarni、S. Chattopadhyay

  DOI：10.1021/jo00118a047

  日期：1995.6

  A convenient chemoenzymatic synthesis for the title methyl branched chiron has been developed starting from 10-undecenoic acid (1). Thus, 1 was converted to 1-(tetrahydropyranyloxy)-10-undecan-2-one (4) which on reaction with triethyl phosphonoacetate and subsequent functionalization led to the racemic chiron 7. This was resolved via C. rugosa lipase-catalyzed acetylation and subsequently used for the syntheses of some chiral insect pheromones. Thus, (S)-7 was mesylated, reduced with LAH and acetylated to give the pheromone (R)-10-methyldodecan-1-yl acetate (I), while its oxidation to the aldehyde 10 followed by Wittig reaction with methylenephosphorane, depyranylation, and hydrogenation gave the alcohol 12. Its tosylation, detosylation, and Hg2+-catalyzed hydration furnished (R)-10-methyltridecan-2-one (II). Likewise, Wittig reaction of (R)-10 with a suitable phosphorane and similar protocol as above afforded the alcohol 14. Its tosylate was coupled with 3-butenylmagnesium bromide to furnish pheromone (S)-14-methyloctadecene (III).