bis[2-(trimethylsilyl)ethyl] (2-exo,3-endo,5-exo,6-exo)-5,6-dihydroxy-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylate | 141849-04-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: bis[2-(trimethylsilyl)ethyl] (2-exo,3-endo,5-exo,6-exo)-5,6-dihydroxy-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylate
• 英文别名: bis<2-(trimethylsilyl)ethyl> (2-exo,3-endo,5-exo,6-exo)-5,6-dihydroxy-7-oxabicyclo<2.2.1>heptane-2,3-dicarboxylate
• CAS: 141849-04-9
• 化学式: C₁₈H₃₄O₇Si₂
• 分子量: 418.635
• InChiKey: FTXXQVXILVPAKK-AYYATWNNSA-N

物化性质

• 沸点：
  478.9±45.0 °C(Predicted)
• 密度：
  1.134±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.48
• 重原子数：
  27.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  102.29
• 氢给体数：
  2.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  bis[2-(trimethylsilyl)ethyl] (2-exo,3-endo,5-exo,6-exo)-5,6-dihydroxy-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylate 在 对甲苯磺酸 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 9.5h， 生成 (+/-)-bis<2-(trimethylsilyl)ethyl> 3β,4β,5β-trihydroxy-1-cyclohexene-1,6-dicarboxylate 3,4-O-acetonide
  参考文献：
  名称：

  The stereocontrolled synthesis of phthalic acid 4,5-cis-dihydrodiol. An unambiguous structural assignment of the bacterial metabolite of phthalic acid

  摘要：

  The stereocontrolled synthesis of the extremely labile phthalic acid 4,5-cis-dihydrodiol (1) has been achieved in a highly efficient manner in seven steps from bis[2-(trimethylsilyl)ethyl] fumarate (2). The Diels-Alder adduct 3 of the fumarate with furan has been converted into first exo-cis-diol 4 and then its acetonide 5. Treatment of acetonide 5 with lithium hexamethyldisilazide results in the regioselective formation of olefinic alcohol 6. Following the introduction of the second double bond into the cyclohexene ring system, the highly sensitive deprotection of the acetonide group of dihydrodiol diester acetonide 7 can be effected under iodine catalysis. The hydrolysis of the 2-(trimethylsilyl)ethyl ester group has been achieved by treatment with tetra(n-butyl)-ammonium fluoride in THF. This synthesis constitutes an unambiguous assignment of the structure and stereochemistry of the microbial metabolite of phthalic acid.

  DOI：

  10.1021/jo00040a023
• 作为产物：
  描述：

  bis<2-(trimethylsilyl)ethyl> (2-exo,3-endo)-7-oxabicyclo<2.2.1>hept-5-ene-2,3-dicarboxylate 在 四氧化锇 十二/十四烷基二甲基氧化胺 作用下， 以 丙酮 、 叔丁醇 为溶剂， 以80%的产率得到bis[2-(trimethylsilyl)ethyl] (2-exo,3-endo,5-exo,6-exo)-5,6-dihydroxy-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylate
  参考文献：
  名称：

  The stereocontrolled synthesis of phthalic acid 4,5-cis-dihydrodiol. An unambiguous structural assignment of the bacterial metabolite of phthalic acid

  摘要：

  The stereocontrolled synthesis of the extremely labile phthalic acid 4,5-cis-dihydrodiol (1) has been achieved in a highly efficient manner in seven steps from bis[2-(trimethylsilyl)ethyl] fumarate (2). The Diels-Alder adduct 3 of the fumarate with furan has been converted into first exo-cis-diol 4 and then its acetonide 5. Treatment of acetonide 5 with lithium hexamethyldisilazide results in the regioselective formation of olefinic alcohol 6. Following the introduction of the second double bond into the cyclohexene ring system, the highly sensitive deprotection of the acetonide group of dihydrodiol diester acetonide 7 can be effected under iodine catalysis. The hydrolysis of the 2-(trimethylsilyl)ethyl ester group has been achieved by treatment with tetra(n-butyl)-ammonium fluoride in THF. This synthesis constitutes an unambiguous assignment of the structure and stereochemistry of the microbial metabolite of phthalic acid.

  DOI：

  10.1021/jo00040a023