2-<(Z)-4-hepten-1-yl>-2,5,5-trimethyl-1,3-dioxane | 141171-84-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-<(Z)-4-hepten-1-yl>-2,5,5-trimethyl-1,3-dioxane
• 英文别名: 2-[(Z)-hept-4-enyl]-2,5,5-trimethyl-1,3-dioxane
• CAS: 141171-84-8
• 化学式: C₁₄H₂₆O₂
• 分子量: 226.359
• InChiKey: GETVDBLRFGFIKQ-SREVYHEPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.91
• 重原子数：
  16.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2-<(Z)-4-hepten-1-yl>-2,5,5-trimethyl-1,3-dioxane 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以100%的产率得到2-<(Z)-4,5-epoxyhept-1-yl>-2,5,5-trimethyl-1,3-dioxane
  参考文献：
  名称：

  Mechanism of brevicomin biosynthesis from (Z)-6-nonen-2-one in a bark beetle

  摘要：

  We have recently shown that (Z)-6-nonen-2-one serves in vivo as a precursor of the widely occurring bark beetle pheromone (+)-exo-brevicomin. The objective of this study was to determine the biochemical mechanism of this transformation. A novel application of stable isotope labeling techniques, involving the incorporation of the stable isotope O-18 from labeled water and oxygen, has now been used to determine the nature of the biosynthetic intermediate and the stereochemistry of the biochemical transformation. The mountain pine beetle (MPB), Dendroctonus ponderosae Hopkins, was used as the test insect. MPBs exposed to [O-18]oxygen gas produced exo-brevicomin that was enriched in two atoms of O-18/molecule, indicating that both oxygens of exo-brevicomin were derived from molecular oxygen. These results indicated that the conversion of (Z)-6-nonen-2-one to (+)-exo-brevicomin proceeded through a keto epoxide intermediate and that the epoxide was not converted to a diol prior to the cyclization. Labeling studies with [O-18]oxygen gas and [O-18]water indicated that the conversion of the keto epoxide to (+)-exo-brevicomin in MPBs proceeded through both enantiomers of the keto epoxide derivative of (Z)-6-nonen-2-one, (6S,7R)-and (6R,7S)-6,7-epoxynonan-2-one. The route through the (6S,7R) keto epoxide was favored in males, while that through the (6R,7S) keto epoxide was favored in females.

  DOI：

  10.1021/ja00039a019
• 作为产物：
  描述：

  壬-6-烯-2-酮 、 2,2-二甲基-1,3-丙二醇 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 以95%的产率得到2-<(Z)-4-hepten-1-yl>-2,5,5-trimethyl-1,3-dioxane
  参考文献：
  名称：

  Mechanism of brevicomin biosynthesis from (Z)-6-nonen-2-one in a bark beetle

  摘要：

  We have recently shown that (Z)-6-nonen-2-one serves in vivo as a precursor of the widely occurring bark beetle pheromone (+)-exo-brevicomin. The objective of this study was to determine the biochemical mechanism of this transformation. A novel application of stable isotope labeling techniques, involving the incorporation of the stable isotope O-18 from labeled water and oxygen, has now been used to determine the nature of the biosynthetic intermediate and the stereochemistry of the biochemical transformation. The mountain pine beetle (MPB), Dendroctonus ponderosae Hopkins, was used as the test insect. MPBs exposed to [O-18]oxygen gas produced exo-brevicomin that was enriched in two atoms of O-18/molecule, indicating that both oxygens of exo-brevicomin were derived from molecular oxygen. These results indicated that the conversion of (Z)-6-nonen-2-one to (+)-exo-brevicomin proceeded through a keto epoxide intermediate and that the epoxide was not converted to a diol prior to the cyclization. Labeling studies with [O-18]oxygen gas and [O-18]water indicated that the conversion of the keto epoxide to (+)-exo-brevicomin in MPBs proceeded through both enantiomers of the keto epoxide derivative of (Z)-6-nonen-2-one, (6S,7R)-and (6R,7S)-6,7-epoxynonan-2-one. The route through the (6S,7R) keto epoxide was favored in males, while that through the (6R,7S) keto epoxide was favored in females.

  DOI：

  10.1021/ja00039a019

文献信息

• Mechanism of brevicomin biosynthesis from (Z)-6-nonen-2-one in a bark beetle
  作者：Desiree Vanderwel、A. Cameron Oehlschlager

  DOI：10.1021/ja00039a019

  日期：1992.6

  We have recently shown that (Z)-6-nonen-2-one serves in vivo as a precursor of the widely occurring bark beetle pheromone (+)-exo-brevicomin. The objective of this study was to determine the biochemical mechanism of this transformation. A novel application of stable isotope labeling techniques, involving the incorporation of the stable isotope O-18 from labeled water and oxygen, has now been used to determine the nature of the biosynthetic intermediate and the stereochemistry of the biochemical transformation. The mountain pine beetle (MPB), Dendroctonus ponderosae Hopkins, was used as the test insect. MPBs exposed to [O-18]oxygen gas produced exo-brevicomin that was enriched in two atoms of O-18/molecule, indicating that both oxygens of exo-brevicomin were derived from molecular oxygen. These results indicated that the conversion of (Z)-6-nonen-2-one to (+)-exo-brevicomin proceeded through a keto epoxide intermediate and that the epoxide was not converted to a diol prior to the cyclization. Labeling studies with [O-18]oxygen gas and [O-18]water indicated that the conversion of the keto epoxide to (+)-exo-brevicomin in MPBs proceeded through both enantiomers of the keto epoxide derivative of (Z)-6-nonen-2-one, (6S,7R)-and (6R,7S)-6,7-epoxynonan-2-one. The route through the (6S,7R) keto epoxide was favored in males, while that through the (6R,7S) keto epoxide was favored in females.