5-endo-<<(tert-butyldimethylsilyl)oxy>methyl>-2-(4'-methylbenzenesulfonyl)-3-oxo-2-azabicyclo<2.2.2>oct-7-ene | 141667-51-8

• 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: 5-endo-<<(tert-butyldimethylsilyl)oxy>methyl>-2-(4'-methylbenzenesulfonyl)-3-oxo-2-azabicyclo<2.2.2>oct-7-ene
• 英文别名: 5-endo-{[(tert-butyldimethylsilyl)oxy]methyl}-2-(4'-methylbenzenesulfonyl)-3-oxo-2-azabicyclo[2.2.2]oct-7-ene；(1S,4S,8S)-8-[[tert-butyl(dimethyl)silyl]oxymethyl]-2-(4-methylphenyl)sulfonyl-2-azabicyclo[2.2.2]oct-5-en-3-one
• CAS: 141667-51-8
• 化学式: C₂₁H₃₁NO₄SSi
• 分子量: 421.633
• InChiKey: WVFGLAHYPRDJTE-LMMKCTJWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.11
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  lithium methanolate 、 5-endo-<<(tert-butyldimethylsilyl)oxy>methyl>-2-(4'-methylbenzenesulfonyl)-3-oxo-2-azabicyclo<2.2.2>oct-7-ene 以 正己烷 、 二氯甲烷 为溶剂， 反应 4.0h， 以66%的产率得到methyl <<(tert-butyldimethylsilyl)oxy>methyl>-4β-<(4'-methylbenzenesulfonyl)amino>cyclohexene-1-carboxylate
  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-(4"-methylbenzenesulfenyl)-2-(4'-methylbenzenesulfonyl)-3-oxo-2-azabicyclo<2.2.2>oct-7-ene-5-endo-carboxaldehyde 在 sodium tetrahydroborate 、 偶氮二异丁腈 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 2.33h， 生成 5-endo-<<(tert-butyldimethylsilyl)oxy>methyl>-2-(4'-methylbenzenesulfonyl)-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.