endo,endo-9-oxabicyclo[4.2.1]nonane-2,5-diol | 19740-86-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: endo,endo-9-oxabicyclo[4.2.1]nonane-2,5-diol
• 英文别名: (endo,endo)-9-oxabicyclo[4.2.1]nonane-2,5-diol；endo,endo-2,5-Dihydroxy-9-oxabicyclo<4.2.1>nonan；(1r,2r,5s,6s)-9-Oxabicyclo[4.2.1]nonane-2,5-diol；(1S,2S,5R,6R)-9-oxabicyclo[4.2.1]nonane-2,5-diol
• CAS: 19740-86-4
• 化学式: C₈H₁₄O₃
• 分子量: 158.197
• InChiKey: GJZQHDOUUCAZHY-KVFPUHGPSA-N

物化性质

• 沸点：
  325.3±27.0 °C(Predicted)
• 密度：
  1.258±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  乙酸乙烯酯 、 endo,endo-9-oxabicyclo[4.2.1]nonane-2,5-diol 在 磷脂酶B 作用下， 生成 (1R,2R,5S,6S)-(+)-2-acetoxy-9-oxa-bicyclo[4.2.1]nonan-5-ol 、 endo,endo-2,5-diacetoxy-9-oxabicyclo[4.2.1]nonane
  参考文献：
  名称：

  Selectivity of Candida rugosa lipase in simultaneous separation of skeletal isomers, desymmetrization, and kinetic racemate cleavage of 9-oxabicyclononanediols

  摘要：

  The diols 2 and 3, available in one step from cycloocta-1,5-diene, are selectively acetylated at the (R)-centers using Candida rugosa lipase to give the corresponding enantiopure compounds. In contrast, the (S,S)-enantiomer of 11 is transformed under identical conditions. The stereoselectivity of the lipase has been investigated by modeling of the transition state geometries at the active site of the enzyme. (C) 2003 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(02)02876-9
• 作为产物：
  描述：

  1,5-cis,cis-cyclooctadiene 在 过氧乙酸 、 溶剂黄146 、 sodium hydroxide 作用下， 以 水 为溶剂， 生成 endo,endo-9-oxabicyclo[4.2.1]nonane-2,5-diol 、 9-氧杂双环[3.3.1]壬烷-2,6-二醇
  参考文献：
  名称：

  跨环O-杂环化：一种有用的工具，用于合成Murisolin和16,19-顺式-Murisolin

  摘要：

  跨环O-杂环化被用作总合成中的关键步骤。这种高度立体选择性和无金属的转换一步就引入了四个立体中心。它被选为合成Murisolin和16,19-顺式-Murisolin，这两种无水产乙酸原素的关键步骤。两种合成路线的立体发散后期分离进一步说明了这种合成的效率。

  DOI：

  10.1021/ol302820c

文献信息

• Synthesis of Enantiopure 9-Oxabicyclononanediol Derivatives by Lipase-Catalyzed Transformations and Determination of Their Absolute Configuration
  作者：Klaus Hegemann、Roland Fröhlich、Günter Haufe

  DOI：10.1002/ejoc.200300783

  日期：2004.5

  shape is responsible for the observed stereoselectivity of the lipases for the racemic endo,endo compounds (±)-3 and (±)-7 on the one hand and the exo,exo compound (±)-12 on the other hand. The absolute configuration and crystal packing of the products was determined by X-ray structural analysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  Endo,endo-9-oxabicyclo[4.2.1]nonane-2,5-diol (meso-2) 和endo,endo-9-oxabicyclo[3.3.1]nonane-2,6-diol [(±) -3] 由环辛基-1,5-二烯 (1) 在用过酸处理后通过跨环 O-杂环化和随后皂化形成的二醇单酯如 (±)-4 和 (±)-5 制备。相应的二乙酸酯，meso-6 和 (±)-7，是通过 meso-2 和 (±)-3 或 (±)-4 和 (±)-5 与乙酸酐/吡啶乙酰化形成的。这些二乙酸酯被微生物酶如来自南极假丝酵母 (CAL) 或红假丝酵母 (CRL) 的脂肪酶对映选择性水解。相应的对映异构体是通过脂肪酶催化的二醇 meso-2 和 (±)-3 与乙酸乙烯酯的乙酰化形成的。骨架异构体也可以通过这种方式分离，因为对映纯的单乙酸酯 4 是由内消旋化合物 2 或 6 形成的，而外消旋二乙酸酯
• Transannular <i>O</i>-Heterocyclization: A Useful Tool for the Total Synthesis of Murisolin and 16,19-<i>cis</i>-Murisolin
  作者：Peter Persich、Julia Kerschbaumer、Sandra Helling、Barbara Hildmann、Birgit Wibbeling、Günter Haufe

  DOI：10.1021/ol302820c

  日期：2012.11.16

  O-heterocyclization is applied as a key step in a total synthesis. This highly stereoselective and metal-free transformation introduces four stereocenters in one step. It was chosen to be the pivotal step in the synthesis of Murisolin and 16,19-cis-Murisolin, two annonaceous acetogenins. The efficiency of this synthesis is further illustrated by a stereodivergent late-stage separation of both synthetic routes

  跨环O-杂环化被用作总合成中的关键步骤。这种高度立体选择性和无金属的转换一步就引入了四个立体中心。它被选为合成Murisolin和16,19-顺式-Murisolin，这两种无水产乙酸原素的关键步骤。两种合成路线的立体发散后期分离进一步说明了这种合成的效率。
• Selectivity of Candida rugosa lipase in simultaneous separation of skeletal isomers, desymmetrization, and kinetic racemate cleavage of 9-oxabicyclononanediols
  作者：Klaus Hegemann、Holger Schimanski、Udo Höweler、Günter Haufe

  DOI：10.1016/s0040-4039(02)02876-9

  日期：2003.3

  The diols 2 and 3, available in one step from cycloocta-1,5-diene, are selectively acetylated at the (R)-centers using Candida rugosa lipase to give the corresponding enantiopure compounds. In contrast, the (S,S)-enantiomer of 11 is transformed under identical conditions. The stereoselectivity of the lipase has been investigated by modeling of the transition state geometries at the active site of the enzyme. (C) 2003 Published by Elsevier Science Ltd.