(3S,3aS,5aR,9aR,9bS)-3-Methyl-9-methylene-5a-(S)-oxiranyl-octahydro-furo[2,3-f]isochromene-2,8-dione | 454245-89-7

• 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: (3S,3aS,5aR,9aR,9bS)-3-Methyl-9-methylene-5a-(S)-oxiranyl-octahydro-furo[2,3-f]isochromene-2,8-dione
• 英文别名: (3S,3aS,5aR,9aR,9bS)-3-methyl-9-methylidene-5a-[(2S)-oxiran-2-yl]-3a,4,5,6,9a,9b-hexahydro-3H-furo[2,3-f]isochromene-2,8-dione
• CAS: 454245-89-7
• 化学式: C₁₅H₁₈O₅
• 分子量: 278.305
• InChiKey: QHLMBVZRVFJOCQ-IOJWBFAVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3S,3aS,5aR,9aR,9bS)-3-Methyl-9-methylene-5a-(S)-oxiranyl-octahydro-furo[2,3-f]isochromene-2,8-dione 在 potassium selenocyanate 作用下， 以 水 、 叔丁醇 为溶剂， 反应 6.0h， 以71%的产率得到(3S,3aS,5aR,9aS,9bS)-3-methyl-9-methylene-5a-vinyldecahydrofuro<2,3-f><2>benzopyran-2,8-dione
  参考文献：
  名称：

  Synthesis of (+)-8-Deoxyvernolepin and Its 11,13-Dihydroderivative. A Novel Reaction Initiated by Sulfene Elimination Leads to the 2-Oxa-cis-decalin Skeleton

  摘要：

  The title compounds are interesting candidates for antifungal screening. This paper describes the enantiospecific synthesis of these compounds starting from (+)-costunolide isolated from a commercially available extract. We used two novel reactions as key synthetic steps in this work: the acid-induced cyclization of an delta,epsilon-epoxy ester, which stereoselectively gave a hydroxymethyl-substituted delta-lactone, with the hydroxyalkyl group in the desired beta-equatorial disposition, and a reaction cascade, initiated by a base-promoted sulfene elimination, which led to a 10-oxiranyl-2-oxa-cis-decalin from the mesylate of a trans-fused delta-lactone. We also found that the reaction between selenium dioxide and the 1,5-diene system of elemanolides gave selenadecalins analogous to natural eudesmanolides. Our results prove that the synthetic strategy employed, on the basis of biomimetic concepts, is a useful procedure for the enantiospecific preparation of (+)-vernolepin-related compounds from accessible germacrolides.

  DOI：

  10.1021/jo0256538
• 作为产物：
  描述：

  木香烃内酯 在 10percent Pd/C sodium chlorite 、 sodium dihydrogenphosphate 、 selenium(IV) oxide 、 2-甲基-2-丁烯 、 三氟化硼乙醚 、 氢气 、 碘 、 二甲基二环氧乙烷 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 mercury(II) oxide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 四氯化碳 、 二氯甲烷 、 水 、 丙酮 、 叔丁醇 为溶剂， 反应 62.25h， 生成 (3S,3aS,5aR,9aR,9bS)-3-Methyl-9-methylene-5a-(S)-oxiranyl-octahydro-furo[2,3-f]isochromene-2,8-dione
  参考文献：
  名称：

  Synthesis of (+)-8-Deoxyvernolepin and Its 11,13-Dihydroderivative. A Novel Reaction Initiated by Sulfene Elimination Leads to the 2-Oxa-cis-decalin Skeleton

  摘要：

  The title compounds are interesting candidates for antifungal screening. This paper describes the enantiospecific synthesis of these compounds starting from (+)-costunolide isolated from a commercially available extract. We used two novel reactions as key synthetic steps in this work: the acid-induced cyclization of an delta,epsilon-epoxy ester, which stereoselectively gave a hydroxymethyl-substituted delta-lactone, with the hydroxyalkyl group in the desired beta-equatorial disposition, and a reaction cascade, initiated by a base-promoted sulfene elimination, which led to a 10-oxiranyl-2-oxa-cis-decalin from the mesylate of a trans-fused delta-lactone. We also found that the reaction between selenium dioxide and the 1,5-diene system of elemanolides gave selenadecalins analogous to natural eudesmanolides. Our results prove that the synthetic strategy employed, on the basis of biomimetic concepts, is a useful procedure for the enantiospecific preparation of (+)-vernolepin-related compounds from accessible germacrolides.

  DOI：

  10.1021/jo0256538

文献信息

• Synthesis of (+)-8-Deoxyvernolepin and Its 11,13-Dihydroderivative. A Novel Reaction Initiated by Sulfene Elimination Leads to the 2-Oxa-<i>cis</i>-decalin Skeleton
  作者：Alejandro F. Barrero、J. Enrique Oltra、Míriam Álvarez、Antonio Rosales

  DOI：10.1021/jo0256538

  日期：2002.8.1

  The title compounds are interesting candidates for antifungal screening. This paper describes the enantiospecific synthesis of these compounds starting from (+)-costunolide isolated from a commercially available extract. We used two novel reactions as key synthetic steps in this work: the acid-induced cyclization of an delta,epsilon-epoxy ester, which stereoselectively gave a hydroxymethyl-substituted delta-lactone, with the hydroxyalkyl group in the desired beta-equatorial disposition, and a reaction cascade, initiated by a base-promoted sulfene elimination, which led to a 10-oxiranyl-2-oxa-cis-decalin from the mesylate of a trans-fused delta-lactone. We also found that the reaction between selenium dioxide and the 1,5-diene system of elemanolides gave selenadecalins analogous to natural eudesmanolides. Our results prove that the synthetic strategy employed, on the basis of biomimetic concepts, is a useful procedure for the enantiospecific preparation of (+)-vernolepin-related compounds from accessible germacrolides.