4-(4'-methylbenzenesulfenyl)-5-exo-nitro-3-oxo-2-oxabicyclo<2.2.2>oct-7-ene | 141553-87-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 4-(4'-methylbenzenesulfenyl)-5-exo-nitro-3-oxo-2-oxabicyclo<2.2.2>oct-7-ene
• 英文别名: (1R,4S,8S)-4-(4-methylphenyl)sulfanyl-8-nitro-2-oxabicyclo[2.2.2]oct-5-en-3-one
• CAS: 141553-87-9
• 化学式: C₁₄H₁₃NO₄S
• 分子量: 291.328
• InChiKey: YPZLSQGYJBBJKH-JKOKRWQUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  97.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  4-(4'-methylbenzenesulfenyl)-5-endo-nitro-3-oxo-2-oxabicyclo<2.2.2>oct-7-ene 在 palladium on activated charcoal 甲酸铵 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 22.0h， 以65%的产率得到4-(4'-methylbenzenesulfenyl)-5-exo-nitro-3-oxo-2-oxabicyclo<2.2.2>oct-7-ene
  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

文献信息

• Diels-Alder cycloadditions using nucleophilic 3-(p-tolylthio)-2-pyrone. Regiocontrolled and stereocontrolled synthesis of unsaturated, bridged, bicyclic lactones
  作者：Gary H. Posner、Todd D. Nelson、Chris M. Kinter、Neil Johnson

  DOI：10.1021/jo00041a009

  日期：1992.7

  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.