(2α,3β(R*))-(+/-)-Tetrahydro-4-methylene-α-<2-(trimethylsilyl)ethoxy>-2-octyl-5-oxo-3-furanacetic acid | 107977-44-6

• 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: (2α,3β(R*))-(+/-)-Tetrahydro-4-methylene-α-<2-(trimethylsilyl)ethoxy>-2-octyl-5-oxo-3-furanacetic acid
• 英文别名: (2α,3β(R^*))-(+/-)-Tetrahydro-4-methylene-α-<2-(trimethylsilyl)ethoxy>-2-octyl-5-oxo-3-furanacetic acid；(2α,3β(R^*))-(+/-)-Tetrahydro-4-methylene-α-[2-(trimethylsilyl)ethoxy]-2-octyl-5-oxo-3-furanacetic acid
• CAS: 107977-44-6
• 化学式: C₂₀H₃₆O₅Si
• 分子量: 384.588
• InChiKey: QTBNIKNJXWLJRC-SQNIBIBYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.64
• 重原子数：
  26.0
• 可旋转键数：
  13.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  (2α,3β(R*))-(+/-)-Tetrahydro-4-methylene-α-<2-(trimethylsilyl)ethoxy>-2-octyl-5-oxo-3-furanacetic acid 在 camphor-10-sulfonic acid 、 三氟化硼乙醚 、 sodium ethanolate 、 间氯过氧苯甲酸 作用下， 以 乙醚 、 二氯甲烷 、 氯仿 、 甲苯 为溶剂， 反应 124.59h， 生成
  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：

  (+/-)-3-<<2-<2-(Trimethylsilyl)ethoxy>acetoxy>methyl>-5-octyl-2(5H)-furanone 在 三甲基氯硅烷 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 以70%的产率得到(2α,3β(R*))-(+/-)-Tetrahydro-4-methylene-α-<2-(trimethylsilyl)ethoxy>-2-octyl-5-oxo-3-furanacetic 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

文献信息

• Total synthesis of (±)-isoavenaciolide and (±)-avenaciolide
  作者：Steven D. Burke、Gregory J. Pacofsky、Anthony D. Piscopio

  DOI：10.1016/s0040-4039(00)84792-9

  日期：1986.1

  The antifungal mold metabolites isoavenaciolide (1b) and avenaciolide (1c) have been synthesized in racemic form from a common precursor, α-methylene lactone 4, obtained via a glycolate ester enolate Claisen rearrangement.

  抗真菌霉菌的代谢产物异阿维酸内酯（1b）和阿维酸内酯（1c）是由一种常见的前体α-亚甲基内酯4以外消旋形式合成的，该前体是通过乙醇酸酯烯醇酸酯Claisen重排获得的。