(1S,3aR,4R,5R,7aR)-1-[(1'R)-1',2'-dihydroxyethyl]-5-methyl-3-oxo-1,3,3a,4,5,7a-hexahydroisobenzofuran-4-carboxylic acid ethyl ester | 937172-57-1

• 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: (1S,3aR,4R,5R,7aR)-1-[(1'R)-1',2'-dihydroxyethyl]-5-methyl-3-oxo-1,3,3a,4,5,7a-hexahydroisobenzofuran-4-carboxylic acid ethyl ester
• 英文别名: ethyl (1S,3aR,4R,5R,7aR,1'R)-1-(1',2'-dihydroxyethyl)-5-methyl-3-oxo-1,3,3a,4,5,7a-hexahydroisobenzofuran-4-carboxylate；ethyl (1S,3aR,4R,5R,7aR)-1-[(1R)-1,2-dihydroxyethyl]-5-methyl-3-oxo-3a,4,5,7a-tetrahydro-1H-2-benzofuran-4-carboxylate
• CAS: 937172-57-1
• 化学式: C₁₄H₂₀O₆
• 分子量: 284.309
• InChiKey: GBTPFQDNXNOVFS-ZKSVUJDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  93.1
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1S,3aR,4R,5R,7aR)-1-[(1'R)-1',2'-dihydroxyethyl]-5-methyl-3-oxo-1,3,3a,4,5,7a-hexahydroisobenzofuran-4-carboxylic acid ethyl ester 在 咪唑 、 碘 、 L-Selectride 、 三苯基膦 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.17h， 生成 (1R,3R,3aR,4R,5R,7aR)-3-hydroxy-5-methyl-1-vinyl-1,3,3a,4,5,7a-hexahydroisobenzofuran-4-carboxylic acid ethyl ester
  参考文献：
  名称：

  Asymmetric Synthesis of the Oxygenated Polycyclic System of (+)-Harringtonolide

  摘要：

  A straightforward asymmetric synthesis of the cage oxygenated structure of (+)-harringtonolide has been accomplished for the first time. The key steps involved (i) a templated stereoselective IMDA reaction to build a highly functionalized cyclohexene ring D, (ii) functionalization of the cycloadduct, (iii) ring-closing metathesis providing the five-membered ring C, and finally (iv) a challenging one-step cascade cyclization of an epoxy-alcohol toward the target structure, whose mechanism was investigated.

  DOI：

  10.1021/ol300133x
• 作为产物：
  描述：

  (-)-(4E,6Z)-(1'R,2R,3S)-1,3-dihydroxy-1,3-O-ethylidene-4,6-octadien-2-yl ethyl fumarate 在 2,6-二叔丁基-4-甲基苯酚 、 水 、 三氟乙酸 作用下， 以 甲苯 为溶剂， 反应 110.5h， 生成 (1S,3aR,4R,5R,7aR)-1-[(1'R)-1',2'-dihydroxyethyl]-5-methyl-3-oxo-1,3,3a,4,5,7a-hexahydroisobenzofuran-4-carboxylic acid ethyl ester
  参考文献：
  名称：

  Utility of a chiral 1,3-dioxane template in stereoselective intramolecular Diels–Alder reactions

  摘要：

  The ethylidene acetal Of D-erythrose was used as a template for stereoselective IMDA reactions: high endo selectivity and yields in favor of the cis product were observed with 1,3,9-trienes, resulting from a boat transition state. For natural product synthesis, the reaction was successfully applied to a diene with terminal Z-olefin. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.02.089

文献信息

• Synthesis of Naturally Occurring Cyclohexene Rings Using Stereodirected Intramolecular Diels-Alder Reactions Through Asymmetric 1,3-Dioxane Tethering
  作者：Hajer Abdelkafi、Laurent Evanno、Alexandre Deville、Lionel Dubost、Angèle Chiaroni、Bastien Nay

  DOI：10.1002/ejoc.201001678

  日期：2011.5

  asymmetric 1,3-dioxane template in intramolecular Diels-Alder reactions is reported. The 1,3,9-decatrienoates substrates gave predominantly the endo-boat products, with minor amounts of the exo-boat isomer. Various substitutions (14 examples) were introduced and the results gave an indication of the scope and also a few limitations of the method. In particular, the approach was applicable to (E,Z)-diene

  报告了容易获得的不对称 1,3-二恶烷模板在分子内 Diels-Alder 反应中的应用。1,3,9-十碳三烯酸酯底物主要产生内型船型产物，少量外型船型异构体。引入了各种替换（14 个示例），结果表明了该方法的范围和一些限制。特别是，该方法适用于 (E,Z)-二烯底物，获得了良好的产率和选择性。通过应用合适的底物，我们描述了用于全合成二萜三萜内酯 (1) 和吡咯烷聚酮化合物 (2) 的有价值中间体的成功合成，在高度官能化的环己烯环系统中提供了天然产物的适当立体化学。
• Synthetic studies toward the cytotoxic norditerpene (+)-harringtonolide: setting up key-stereogenic centers of the cyclohexane ring D
  作者：Hajer Abdelkafi、Laurent Evanno、Patrick Herson、Bastien Nay

  DOI：10.1016/j.tetlet.2011.04.101

  日期：2011.7

  (+)-harringtonolide were installed by functionalization of an enantiomerically pure IMDA cycloadduct, constructed from the chiral pool. The chiral 1,3-dioxane template used to direct the IMDA reaction was unraveled in an acidic medium, through spectacular hydrolysis of the acetal and concomitant lactone ring contraction. The central cyclohexene was selectively epoxidized either on the β- or on the α-side

  （+）-harringtonolide不对称循环D的关键立体生成中心是通过手性池中构建的对映体纯IMDA环加合物的功能化安装的。通过缩醛的惊人水解和伴随的内酯环收缩，在酸性介质中解开了用于指导IMDA反应的手性1,3-二恶烷模板。取决于取代方式，中央环己烯在β-侧或α-侧上选择性地环氧化。几种环氧化物中间体的反应性受到了harringtonolide氧化桥的构建的挑战。我们发现其中一种适合获取另一种天然产品四溴新霉素，其与harringtonolide具有相似的替代方式。另外，功能化导致建立关键立体中心，在途中合成了harringtonolide的不对称合成。环氧中间体的反应性为该全合成的未来工作提供了有益的见识。