Acetic acid (1S,3S,4R,5S)-7,7-difluoro-4-(imidazole-1-carbothioyloxymethyl)-2,6-dioxa-bicyclo[3.1.1]hept-3-ylmethyl ester | 147091-42-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: Acetic acid (1S,3S,4R,5S)-7,7-difluoro-4-(imidazole-1-carbothioyloxymethyl)-2,6-dioxa-bicyclo[3.1.1]hept-3-ylmethyl ester
• 英文别名: [(1S,3S,4R,5S)-7,7-difluoro-4-(imidazole-1-carbothioyloxymethyl)-2,6-dioxabicyclo[3.1.1]heptan-3-yl]methyl acetate
• CAS: 147091-42-7
• 化学式: C₁₃H₁₄F₂N₂O₅S
• 分子量: 348.327
• InChiKey: JLOIWNTUGKNKQX-ZNSHCXBVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  Acetic acid (1S,3S,4R,5S)-7,7-difluoro-4-(imidazole-1-carbothioyloxymethyl)-2,6-dioxa-bicyclo[3.1.1]hept-3-ylmethyl ester 在 吡啶 、 4-二甲氨基吡啶 、 4 A molecular sieve 、 碳酸氢钠 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 80.0h， 生成 (1S,3S,4R,5S)-4-(cyanomethyl)-5-(acetoxymethyl)-7,7-difluoro-2,6-dioxabicyclo<3.1.1>heptane
  参考文献：
  名称：

  Enantio- and regiospecific partial hydrolysis of racemic diol diacetates by pig liver esterase

  摘要：

  The high enantio- and regiospecificity reported from this laboratory for the hydrolysis of the diacetate (+/-)-2 with pig liver esterase to yield enantiomericly pure monoacetate (+)-3a has been investigated further to define some of the structural features responsible for this unusual degree of specificity. The hydrolysis of the isomeric (+/-)-5 was found to proceed with identical specificity both qualitatively and quantitatively, indicating that the enzyme recognizes the overall geometry of these substrates but is unable to distinguish between the CF2 group and the oxygen bridge. Partial hydrolysis of the monocyclic diacetate (+/-)-16 showed parallel enantioselectivity but proceeded with only 25% ee. These data indicate that the highly rigid 2 and 5 which present sterically well-defined targets to the enzyme result in the isolation of a single regioisomer and enantiomer as the major products of this reaction. In contrast, the conformational flexibility of 16 leads to poor differentiation between the rates of hydrolysis of the two enantiomers resulting in a low ee. It is concluded that conformationally stable molecules may offer favorable targets for regio and/or enantioselectivity in PLE reactions.

  DOI：

  10.1021/jo00059a046
• 作为产物：
  描述：

  (1SR,3SR,4RS,5SR)-4,5-bis(hydroxymethyl)-7,7-difluoro-2,6-dioxabicyclo<3.1.1>heptane 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.17h， 生成 Acetic acid (1S,3S,4R,5S)-7,7-difluoro-4-(imidazole-1-carbothioyloxymethyl)-2,6-dioxa-bicyclo[3.1.1]hept-3-ylmethyl ester
  参考文献：
  名称：

  Enantio- and regiospecific partial hydrolysis of racemic diol diacetates by pig liver esterase

  摘要：

  The high enantio- and regiospecificity reported from this laboratory for the hydrolysis of the diacetate (+/-)-2 with pig liver esterase to yield enantiomericly pure monoacetate (+)-3a has been investigated further to define some of the structural features responsible for this unusual degree of specificity. The hydrolysis of the isomeric (+/-)-5 was found to proceed with identical specificity both qualitatively and quantitatively, indicating that the enzyme recognizes the overall geometry of these substrates but is unable to distinguish between the CF2 group and the oxygen bridge. Partial hydrolysis of the monocyclic diacetate (+/-)-16 showed parallel enantioselectivity but proceeded with only 25% ee. These data indicate that the highly rigid 2 and 5 which present sterically well-defined targets to the enzyme result in the isolation of a single regioisomer and enantiomer as the major products of this reaction. In contrast, the conformational flexibility of 16 leads to poor differentiation between the rates of hydrolysis of the two enantiomers resulting in a low ee. It is concluded that conformationally stable molecules may offer favorable targets for regio and/or enantioselectivity in PLE reactions.

  DOI：

  10.1021/jo00059a046