methyl 4-(4'-methylbenzenesulfenyl)-3-oxo-2-oxabicyclo<2.2.2>oct-7-ene-5-exo-methyl-5-endo-carboxylate | 141510-36-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: methyl 4-(4'-methylbenzenesulfenyl)-3-oxo-2-oxabicyclo<2.2.2>oct-7-ene-5-exo-methyl-5-endo-carboxylate
• 英文别名: methyl (1R,4S,5S)-5-methyl-4-(4-methylphenyl)sulfanyl-3-oxo-2-oxabicyclo[2.2.2]oct-7-ene-5-carboxylate
• CAS: 141510-36-3
• 化学式: C₁₇H₁₈O₄S
• 分子量: 318.394
• InChiKey: JNFANMMHYSFLBV-AFAVFJNCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  77.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  3-(p-tolylthio)-2-pyrone 、 甲基丙烯酸甲酯 以 苯 为溶剂， 反应 216.0h， 以42%的产率得到methyl 4-(4'-methylbenzenesulfenyl)-3-oxo-2-oxabicyclo<2.2.2>oct-7-ene-5-exo-methyl-5-endo-carboxylate
  参考文献：
  名称：

  Diels-Alder cycloadditions using nucleophilic 3-(p-tolylthio)-2-pyrone. Regiocontrolled and stereocontrolled synthesis of unsaturated, bridged, bicyclic lactones

  摘要：

  Captodative 3-(tolylthio)-2-pyrone (1) is shown to be reactive as a nucleophilic diene undergoing 2 + 4-cycloadditions with various electrophilic alkenes under sufficiently mild thermal conditions (less-than-or-equal-to 90-degrees-C) so that the initial bicyclic lactone adducts can be isolated on gram scale in moderate to very good yields (42-82%) without loss of CO2. These bicyclic adducts are formed regiospecifically and often with excellent stereoselectivity. These Diels-Alder cycloadditions are the first examples of a captodative unsaturated sulfide acting as an enophile. NMR data (C-13) are presented correlating the electron density in the pyrone diene systems with their Diels-Alder reactivity, and some transformations of the bicyclic lactone adducts are shown to illustrate the value and versatility of these richly functionalized synthetic intermediates.

  DOI：

  10.1021/jo00041a009