[(9R,10R)-3,4,5,19-tetramethoxyspiro[15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaene-9,2'-oxirane]-10-yl]methyl methanesulfonate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 单宁
• 英文名称: [(9R,10R)-3,4,5,19-tetramethoxyspiro[15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaene-9,2'-oxirane]-10-yl]methyl methanesulfonate
• 化学式: C₂₄H₂₈O₁₀S
• 分子量: 508.546
• InChiKey: AZWAAGMHUSMQJY-MYYSRTQBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  35
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  120
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  (S)-3-<5-methoxy-3,4-(methylenedioxy)benzyl>butanolide 在 盐酸 、 bis-triphenylphosphine-palladium(II) chloride 、 sodium hydroxide 、 甲酸铵 、 三氯化硼 、 二异丁基氢化铝 、 potassium carbonate 、 iron(III) perchlorate 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 [(9R,10R)-3,4,5,19-tetramethoxyspiro[15,17-dioxatetracyclo[10.7.0.02,7.014,18]nonadeca-1(19),2,4,6,12,14(18)-hexaene-9,2'-oxirane]-10-yl]methyl methanesulfonate
  参考文献：
  名称：

  光学纯的gomisin A和五味子素的合成：具有天然结构的gomisin A和五味子素的第一个全合成

  摘要：

  首次完成了具有天然构型的gomisin A和五味子素的全合成。这些合成的关键特征是中间体9和21的高效分子内氧化偶联，可以以光学纯形式的两种对映异构体形式获得。操纵7和22的内酯部分可得到五味子素和gomisin A的天然对映体。

  DOI：

  10.1016/s0040-4039(00)74679-x

文献信息

• Synthesis of Optically Pure Gomisi Lignans: The Total Synthesis of (+)-Schizandrin, (+)-Gomisin A, and (+)-Isoschizandrin in Naturally Occurring Forms
  作者：Masahide Tanaka、Chieko Mukaiyama、Hiroshi Mitsuhashi、Masao Maruno、Takeshi Wakamatsu

  DOI：10.1021/jo00119a010

  日期：1995.7

  The total syntheses of (+)-schizandrin (1), (+)-gomisin A (2), and (+)-isoschizandrin (3) having natural configurations were accomplished. Optically pure butyrolactones ((-)-9, (-)-31) were transformed to alpha-benzylidenebutyrolactones ((+)-10, (+)-32, (+)-35). By a highly efficient iron(III) perchlorate-mediated oxidative coupling reaction of 10, 32, and 35, the key intermediates with biphenyl skeletons ((-)-11, (-)-33) were constructed with high stereoselectivity. Several methods for the stereoselective introduction of the C6-hydroxyl group were examined. For the synthesis of schizandrin and gomisin A, the Mukaiyama hydration reaction of(-)-11 and (-)-33 provided the desired products with satisfactory selectivity. For the synthesis of isoschizandrin, the stereoselective epoxidation of allylic alcohol (+)-48 was successfully utilized taking advantage of its conformational features.
• Synthesis of optically pure gomisin A and schizandrin: The first total synthesis of gomisin A and schizandrin having naturally occurring configurations
  作者：Masahide Tanaka、Chieko Mukaiyama、Hiroshi Mitsuhashi、Takeshi Wakamatsu

  DOI：10.1016/s0040-4039(00)74679-x

  日期：1992.7

  The total synthesis of gomisin A and schizandrin having natural configurations were accomplished for the first time. The key feature of these syntheses is a highly efficient intramolecular oxidative coupling of the intermediates 9 and 21, which can be obtained as both enantiomers in optically pure forms. The manipulation of the lactone moieties of 7 and 22 afforded natural enantiomers of schizandrin

  首次完成了具有天然构型的gomisin A和五味子素的全合成。这些合成的关键特征是中间体9和21的高效分子内氧化偶联，可以以光学纯形式的两种对映异构体形式获得。操纵7和22的内酯部分可得到五味子素和gomisin A的天然对映体。