(3S,3aS,5aR,9aS,9bS)-3-methyl-9-methylene-5a-vinyldecahydrofuro<2,3-f><2>benzopyran-2,8-dione | 117137-95-8

• 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,9aS,9bS)-3-methyl-9-methylene-5a-vinyldecahydrofuro<2,3-f><2>benzopyran-2,8-dione
• 英文别名: (+)-11β,13-dihydro-8-deoxyvernolepin；(3S,3aS,5aR,9aR,9bS)-5a-ethenyl-3-methyl-9-methylidene-3a,4,5,6,9a,9b-hexahydro-3H-furo[2,3-f]isochromene-2,8-dione
• CAS: 117137-95-8
• 化学式: C₁₅H₁₈O₄
• 分子量: 262.306
• InChiKey: SRZNOBRLLGNULS-WHBBUDTDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  木香烃内酯 在 10percent Pd/C 叔丁基过氧化氢 、 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 、 potassium selenocyanate 、 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 、 甲醇 、 四氯化碳 、 二氯甲烷 、 水 、 丙酮 、 叔丁醇 为溶剂， 反应 127.58h， 生成 (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

文献信息

• SYNTHESIS OF (+)-DEOXYVERNOLEPIN
  作者：Masataka Watanabe、Akira Yoshikoshi

  DOI：10.1246/cl.1980.1315

  日期：1980.10.5

  2,3,3aα,4,5,5a,6,9,9aα,9bβ-Decahydro-3α,9α-dimethyl-5aβ-methoxycarbonyl-2-oxonaphtho[2,3-b]furan (2) accessible from α-santonin was transformed into (+)-deoxyvernolepin (1). The preparation of some α-methylenelactones related to 1 has also been described.

  2,3,3aα,4,5,5a,6,9,9aα,9bβ-Decahydro-3α,9α-dimethyl-5aβ-methoxycarbonyl-2-oxonaphtho[2,3-b]furan (2) 可从 α- santonin 转化为 (+)-deoxyvernolepin (1)。一些与 1 相关的 α-亚甲基内酯的制备也有描述。
• Transformation of santonin into(+)-deoxyvernolepin and related dilactones
  作者：Masataka Watanabe、Akira Yoshikoshi

  DOI：10.1039/p19870002833

  日期：——

  unexpected product, (3S,3aS,6R,7S,7aS)-7-[(S)-2-formylethyl]-2-methoxy-3-methyloctahydrobenzofuran-6-spiro-3′-furan-5′-one (13), which served as the key intermediate for the synthesis of (+)-deoxyvernolepin (2) and related unsaturated lactones (4)–(6). Some unsaturated lactones obtained were submitted to a preliminary test for antitumour activity.

  臭氧分解，然后乙酰化（3 S，3a S，5a R，9 R，9a S，9b S）-5a-羟甲基-2-甲氧基-3,9-二甲基-2,3-十氢萘[1,2-由[-]-α-桑顿宁衍生的b ]呋喃（7）产生了意外的产物（3 S，3a S，6 R，7 S，7a S）-7-[（S）-2-甲酰基乙基] -2 -甲氧基-3-甲基八氢苯并呋喃-6-螺环-3'-呋喃-5'-酮（13），是合成（+）-脱氧vernolepin（2）和相关不饱和内酯的关键中间体（4）–（6）。将获得的一些不饱和内酯进行抗肿瘤活性的初步测试。
• WATANABE, MASATAKA;YOSHIKOSHI, AKIRA, J. CHEM. SOC. PERKIN TRANS., 1,(1987) N 12, 2833-2838
  作者：WATANABE, MASATAKA、YOSHIKOSHI, AKIRA

  DOI：——

  日期：——
• 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.