4-hydroxy-5-endo-<<(tert-butyldimethylsilyl)oxy>methyl>-2-(4'-methylbenzesulfonyl)-3-oxo-2-azabicyclo<2.2.2>oct-7-ene | 141667-53-0

• 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-hydroxy-5-endo-<<(tert-butyldimethylsilyl)oxy>methyl>-2-(4'-methylbenzesulfonyl)-3-oxo-2-azabicyclo<2.2.2>oct-7-ene
• 英文别名: 4-hydroxy-5-endo-{[(tert-butyldimethylsilyl)oxy]methyl}-2-(4'-methylbenzesulfonyl)-3-oxo-2-azabicyclo[2.2.2]oct-7-ene
• CAS: 141667-53-0
• 化学式: C₂₁H₃₁NO₅SSi
• 分子量: 437.632
• InChiKey: ASVMSDPZCJUBJV-FIKGOQFSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.22
• 重原子数：
  29.0
• 可旋转键数：
  5.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  83.91
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  lithium methanolate 、 4-hydroxy-5-endo-<<(tert-butyldimethylsilyl)oxy>methyl>-2-(4'-methylbenzesulfonyl)-3-oxo-2-azabicyclo<2.2.2>oct-7-ene 以 甲醇 为溶剂， 反应 2.0h， 以81%的产率得到methyl 6β<<(tert-butyldimethylsilyl)oxy>methyl>-1β-hydroxy-4α-(4'-methylbenzenesulfonamido)cyclohex-2-enecarboxylate
  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：

  4-<(tert-butyldimethylsilyl)oxy>-5-endo-(hydroxymethyl)-2-(4'-methylbenzenesulfonyl)-3-oxo-2-azabicyclo<2.2.2>oct-7-ene 在 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 8.33h， 生成 4-hydroxy-5-endo-<<(tert-butyldimethylsilyl)oxy>methyl>-2-(4'-methylbenzesulfonyl)-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