4-(4"-methylbenzenesulfenyl)-2-(4'-methylbenzenesulfonyl)-5-endo-nitro-3-oxo-2-azabicyclo<2.2.2>oct-7-ene | 141667-46-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-(4"-methylbenzenesulfenyl)-2-(4'-methylbenzenesulfonyl)-5-endo-nitro-3-oxo-2-azabicyclo<2.2.2>oct-7-ene
• 英文别名: (1S,4R,8S)-4-(4-methylphenyl)sulfanyl-2-(4-methylphenyl)sulfonyl-8-nitro-2-azabicyclo[2.2.2]oct-5-en-3-one
• CAS: 141667-46-1
• 化学式: C₂₁H₂₀N₂O₅S₂
• 分子量: 444.532
• InChiKey: QGLDFDDSZLQBNQ-LKUPVBHCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  134
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-(4"-methylbenzenesulfenyl)-2-(4'-methylbenzenesulfonyl)-5-endo-nitro-3-oxo-2-azabicyclo<2.2.2>oct-7-ene 在 ammonium formate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 20.0h， 以95%的产率得到4-(4"-methylbenzenesulfenyl)-2-(4'-methylbenzenesulfonyl)-5-exo-nitro-3-oxo-2-azabicyclo<2.2.2>oct-7-ene
  参考文献：
  名称：

  Diels-Alder cycloadditions using nucleophilic 2-pyridones. Regiocontrolled and stereocontrolled synthesis of unsaturated, bridged, bicyclic lactams

  摘要：

  Captodative 3-oxy-and 3-(tolylthio)-1-tosyl-2-pyridones 1a-1d are shown to be reactive as nucleophilic dienes undergoing 2 + 4-cycloadditions with various electrophilic alkenes under sufficiently mild thermal conditions (90-100-degrees-C) that the initial bicylic lactam adducts can be isolated on gram scale in fair to very good yields (23-83%) without loss of an isocyanate from the heteroatom bridge. These bicyclic adducts are formed with complete regiocontrol and stereocontrol. For pyridone sulfide 1d, 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 pyridone diene systems with their Diels-Alder reactivity, and some transformations of the bicyclic lactam adducts are shown to illustrate the value and versatility of these richly functionalized synthetic intermediates.

  DOI：

  10.1021/jo00041a010
• 作为产物：
  描述：

  3-(4-methylbenzenesulfenyl)-2-pyridone 在 lithium hexamethyldisilazane 作用下， 以 二氯甲烷 为溶剂， 反应 120.0h， 生成 4-(4"-methylbenzenesulfenyl)-2-(4'-methylbenzenesulfonyl)-5-endo-nitro-3-oxo-2-azabicyclo<2.2.2>oct-7-ene
  参考文献：
  名称：

  Diels-Alder cycloadditions using nucleophilic 2-pyridones. Regiocontrolled and stereocontrolled synthesis of unsaturated, bridged, bicyclic lactams

  摘要：

  Captodative 3-oxy-and 3-(tolylthio)-1-tosyl-2-pyridones 1a-1d are shown to be reactive as nucleophilic dienes undergoing 2 + 4-cycloadditions with various electrophilic alkenes under sufficiently mild thermal conditions (90-100-degrees-C) that the initial bicylic lactam adducts can be isolated on gram scale in fair to very good yields (23-83%) without loss of an isocyanate from the heteroatom bridge. These bicyclic adducts are formed with complete regiocontrol and stereocontrol. For pyridone sulfide 1d, 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 pyridone diene systems with their Diels-Alder reactivity, and some transformations of the bicyclic lactam adducts are shown to illustrate the value and versatility of these richly functionalized synthetic intermediates.

  DOI：

  10.1021/jo00041a010

文献信息

• Diels-Alder cycloadditions using nucleophilic 2-pyridones. Regiocontrolled and stereocontrolled synthesis of unsaturated, bridged, bicyclic lactams
  作者：Gary H. Posner、Victoria Vinader、Kamyar Afarinkia

  DOI：10.1021/jo00041a010

  日期：1992.7

  Captodative 3-oxy-and 3-(tolylthio)-1-tosyl-2-pyridones 1a-1d are shown to be reactive as nucleophilic dienes undergoing 2 + 4-cycloadditions with various electrophilic alkenes under sufficiently mild thermal conditions (90-100-degrees-C) that the initial bicylic lactam adducts can be isolated on gram scale in fair to very good yields (23-83%) without loss of an isocyanate from the heteroatom bridge. These bicyclic adducts are formed with complete regiocontrol and stereocontrol. For pyridone sulfide 1d, 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 pyridone diene systems with their Diels-Alder reactivity, and some transformations of the bicyclic lactam adducts are shown to illustrate the value and versatility of these richly functionalized synthetic intermediates.