(R)-((2S,3R)-2-Ethyl-4-methylene-5-oxo-tetrahydro-furan-3-yl)-(2-trimethylsilanyl-ethoxy)-acetic acid | 104206-42-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (R)-((2S,3R)-2-Ethyl-4-methylene-5-oxo-tetrahydro-furan-3-yl)-(2-trimethylsilanyl-ethoxy)-acetic acid
• CAS: 104206-42-0
• 化学式: C₁₄H₂₄O₅Si
• 分子量: 300.427
• InChiKey: KEYGCZSHQHWTMK-QJPTWQEYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  20.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  72.83
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (R)-((2S,3R)-2-Ethyl-4-methylene-5-oxo-tetrahydro-furan-3-yl)-(2-trimethylsilanyl-ethoxy)-acetic acid 在 三氟化硼乙醚 、 sodium ethanolate 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 2.42h， 生成 (R)-((2S,3S,4R)-2-Ethyl-5-oxo-4-phenylsulfanylmethyl-tetrahydro-furan-3-yl)-hydroxy-acetic acid methyl ester
  参考文献：
  名称：

  Synthesis of ethisolide, isoavenaciolide, and avenaciolide

  摘要：

  Syntheses of the trio of related mold metabolites ethisolide (1), isoavenaciolide (2), and avenaciolide (3) in racemic and optically active forms are described. Glycolate Claisen rearrangements governed by chelation control of enolate geometry and diastereofacial bias in the [3,3] shifts establish the functional and stereochemical details in butyrolactone precursors (15b, 22, and 19) of the natural products. Lactone rearrangements via complementary bis(transesterification) (22 --> 23) and carboxylate displacement/lactonization (26 --> 27 --> 3) reactions provided the diastereomeric isoavenaciolide and avenaciolide structures. Differential reactivities among potential transacylation substrates 15a, 15b, 21, 22, 24, and 26 are attributed to steric interactions or strain in bridged bicyclic intermediates 32, 34, and 36.

  DOI：

  10.1021/jo00034a009
• 作为产物：
  描述：

  (2-Trimethylsilanyl-ethoxy)-acetic acid (S)-5-ethyl-2-oxo-2,5-dihydro-furan-3-ylmethyl ester 在 三甲基氯硅烷 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 生成 (R)-((2S,3R)-2-Ethyl-4-methylene-5-oxo-tetrahydro-furan-3-yl)-(2-trimethylsilanyl-ethoxy)-acetic acid
  参考文献：
  名称：

  Synthesis of ethisolide, isoavenaciolide, and avenaciolide

  摘要：

  Syntheses of the trio of related mold metabolites ethisolide (1), isoavenaciolide (2), and avenaciolide (3) in racemic and optically active forms are described. Glycolate Claisen rearrangements governed by chelation control of enolate geometry and diastereofacial bias in the [3,3] shifts establish the functional and stereochemical details in butyrolactone precursors (15b, 22, and 19) of the natural products. Lactone rearrangements via complementary bis(transesterification) (22 --> 23) and carboxylate displacement/lactonization (26 --> 27 --> 3) reactions provided the diastereomeric isoavenaciolide and avenaciolide structures. Differential reactivities among potential transacylation substrates 15a, 15b, 21, 22, 24, and 26 are attributed to steric interactions or strain in bridged bicyclic intermediates 32, 34, and 36.

  DOI：

  10.1021/jo00034a009