(+/-)-ethisolide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃类
• 英文名称: (+/-)-ethisolide
• 英文别名: (3aS,4R,6aS)-4-ethyl-3-methylidene-4,6a-dihydro-3aH-furo[3,4-b]furan-2,6-dione
• 化学式: C₉H₁₀O₄
• 分子量: 182.176
• InChiKey: USWKEJMURBWWQX-VQVTYTSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (3aS,4R,6S,6aS)-4-ethyl-6-hydroxy-3-methylidene-3a,4,6,6a-tetrahydrofuro[3,4-b]furan-2-one 在 四丙基高钌酸铵 、 N-甲基吗啉氧化物 作用下， 以80%的产率得到(+/-)-ethisolide
  参考文献：
  名称：

  Total synthesis of ethisolide from“naked sugars”

  摘要：

  A total synthesis of(+/-)-ethisolide was realized from (+/-)-7-oxybicyclo[2.2.1]hept-5-en-2-one by using a radical cyclization as a kev step.

  DOI：

  10.1016/0040-4039(94)88024-7

文献信息

• The ester enolate claisen rearrangement. Total synthesis of (±)-ethisolide
  作者：Steven D. Burke、Gregory J. Pacofsky

  DOI：10.1016/s0040-4039(00)85501-x

  日期：1986.1

  A total synthesis of the mold metabolite ethisolide (1a) is described, wherein a glycolate ester enolate Claisen rearrangement and an acid-induced intramolecular bis-transesterification are key steps.

  描述了霉菌代谢物乙异氟醚（1a）的全合成，其中乙醇酸酯烯醇酸酯克莱森重排和酸诱导的分子内双酯交换是关键步骤。
• Short total syntheses of the avenaciolide family of natural products
  作者：Sandra Ainsua Martinez、Martin Gillard、Anne-Caroline Chany、Jonathan W. Burton

  DOI：10.1016/j.tet.2018.06.028

  日期：2018.9

  of natural products are small α-methylene bis-γ-lactones that exhibit a wide variety of biological activities. Herein we report concise syntheses of five members of this family of natural products along with the synthesis of one non-natural analogue. The syntheses proceed in five or six steps from simple, commercially available compounds and feature a key oxidative cyclization/lactonization reaction

  天然产物阿文酸内酯是小的α-亚甲基双-γ-内酯，具有多种生物活性。在此，我们报告了该天然产物家族的五种成员的简明合成以及一种非天然类似物的合成。从简单的可商购化合物开始，合成过程分五步或六步进行，并且具有可能通过自由基机理发生的关键氧化环化/内酯化反应。
• Synthesis of (±)-isoavenaciolide and of (±)-ethisolide from (±)-7-oxabicyclo[2.2.1]hept-5-en-2-one.
  作者：Janine Cossy、Jean-Luc Ranaivosata、Véronique Bellosta

  DOI：10.1016/0040-4020(95)00901-9

  日期：1996.1

  A short total synthesis of (±)-ethisolide and (±)-isoavenaciolide was accomplished from (±)-oxanorbornenone respectively in 11 and 12 steps, using a radical cyclization as a key step.

  使用自由基环化作为关键步骤，分别由（±）-氧杂甲炔酮通过11个步骤和12个步骤完成了（±）-乙内酯和（±）-异文酸内酯的短时全合成。
• Synthesis of ethisolide, isoavenaciolide, and avenaciolide
  作者：Steven D. Burke、Gregory J. Pacofsky、Anthony D. Piscopio

  DOI：10.1021/jo00034a009

  日期：1992.4

  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.
• Total synthesis of ethisolide from“naked sugars”
  作者：Janine Cossy、Jean-Luc Ranaivosata、Véronique Bellosta

  DOI：10.1016/0040-4039(94)88024-7

  日期：1994.2

  A total synthesis of(+/-)-ethisolide was realized from (+/-)-7-oxybicyclo[2.2.1]hept-5-en-2-one by using a radical cyclization as a kev step.