(2E,4S,12R)-4-(tert-Butyldimethylsiloxy)-2-tridecen-12-olide | 152897-13-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: (2E,4S,12R)-4-(tert-Butyldimethylsiloxy)-2-tridecen-12-olide
• CAS: 152897-13-7
• 化学式: C₁₉H₃₆O₃Si
• 分子量: 340.579
• InChiKey: RLODCEVQQKPYHT-LTWOGSJMSA-N

物化性质

• 沸点：
  418.5±38.0 °C(predicted)
• 密度：
  0.94±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.61
• 重原子数：
  23.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (2E,4S,12R)-4-(tert-Butyldimethylsiloxy)-2-tridecen-12-olide 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以66%的产率得到(E)-Homopatulolide C
  参考文献：
  名称：

  Total synthesis of patulolide C and its homo-, nor, and iso analogs

  摘要：

  The stereospecific total synthesis of the naturally occurring macrolide patulolide C 19Eb as well as its iso, nor, and homo analogs is described by applying the photoinduced rearrangement of enantiomerically pure epoxy diazomethyl ketones 14 to gamma-hydroxy alpha,beta-unsaturated esters 15 as the key step. The required epoxy diazomethyl ketones 14 are obtained by a Sharpless epoxidation of an appropriate allylic alcohol, followed by ruthenium tetraoxide oxidation to an oxiranecarboxylic acid, conversion into a mixed anhydride, and treatment with diazomethane. Macrolide 19Zb, which is a geometrical isomer of 19Eb, turned out to be a diastereomer of natural macrolide isopatulolide C, which implies the 4R,11R configuration for this natural material. X-ray diffraction analyses of 19Ea and 19Eb show that there is a considerable difference in spatial arrangement; particularly, the different torsion angles between the carbonyl and olefinic bonds are note worthy. The conformational behavior of these macrolides is also deduced from the NMR and UV spectra.

  DOI：

  10.1021/jo00077a047
• 作为产物：
  描述：

  Ethyl (2E/Z,4S,12R)-12-acetoxy-4-hydroxy-2-tridecenoate 在 4-二甲氨基吡啶 咪唑 、 4-二甲氨基吡啶 、 sodium hydroxide 、 三乙胺 、 2,6-二氯苯甲酰氯 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 50.5h， 生成 (2E,4S,12R)-4-(tert-Butyldimethylsiloxy)-2-tridecen-12-olide
  参考文献：
  名称：

  Total synthesis of patulolide C and its homo-, nor, and iso analogs

  摘要：

  The stereospecific total synthesis of the naturally occurring macrolide patulolide C 19Eb as well as its iso, nor, and homo analogs is described by applying the photoinduced rearrangement of enantiomerically pure epoxy diazomethyl ketones 14 to gamma-hydroxy alpha,beta-unsaturated esters 15 as the key step. The required epoxy diazomethyl ketones 14 are obtained by a Sharpless epoxidation of an appropriate allylic alcohol, followed by ruthenium tetraoxide oxidation to an oxiranecarboxylic acid, conversion into a mixed anhydride, and treatment with diazomethane. Macrolide 19Zb, which is a geometrical isomer of 19Eb, turned out to be a diastereomer of natural macrolide isopatulolide C, which implies the 4R,11R configuration for this natural material. X-ray diffraction analyses of 19Ea and 19Eb show that there is a considerable difference in spatial arrangement; particularly, the different torsion angles between the carbonyl and olefinic bonds are note worthy. The conformational behavior of these macrolides is also deduced from the NMR and UV spectra.

  DOI：

  10.1021/jo00077a047