(+/-)-(1R*,6S*,8R*,9S*,11S*)-9,11-Bis(methoxymethoxy)-6-methyl-2-methylene-12-oxatricyclo<6.3.1.0^1,6>dodecane

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-(1R*,6S*,8R*,9S*,11S*)-9,11-Bis(methoxymethoxy)-6-methyl-2-methylene-12-oxatricyclo<6.3.1.0^1,6>dodecane
• 英文别名: (1S,6S,8R,9S,11S)-9,11-bis(methoxymethoxy)-6-methyl-2-methylidene-12-oxatricyclo[6.3.1.01,6]dodecane
• 化学式: C₁₇H₂₈O₅
• 分子量: 312.406
• InChiKey: DHCHBNCUHVZJSK-BQJWPVKWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (+/-)-(1R*,6S*,8R*,9S*,11S*)-9,11-Bis(methoxymethoxy)-6-methyl-2-methylene-12-oxatricyclo<6.3.1.0^1,6>dodecane 在 氨 、 sodium 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以74%的产率得到(+/-)-(4S*,5R*,7S*)-7,11-Dimethyl-5-hydroxy-4-(methoxymethoxy)-1(11)-bicyclo<5.4.0>undecene
  参考文献：
  名称：

  Functionalization and Utility of Bridging Ethers in the Transformations of Bicyclo[5.4.0]undecanes

  摘要：

  Studies detail the formation and utility of bridged ethers of bicyclo[5.4.0]undecanes as a means for stereocontrolled functionalization as described in a survey of conjugate additions, reductions, and oxidative cyclizations. The intramolecular dipolar cycloaddition of 3-oxidopyrylium ylides affords a facile preparation of the starting trans-fused bicyclo[5.4.0]undecenone 1. Efficient methods toward highly oxygenated bicycloundecanes are described via the highly selective reductive cleavage of 12-oxatricyclo[6.3.1.0(1,6)]dodecanes such as 20 and 21. Reclosure of the era-bridge was examined. Vanadium-catalyzed oxidative reclosure of 24 led exclusively to the novel 2-oxatricyclo[5.4.1.0(3,8)]dodecane system 31.

  DOI：

  10.1021/jo00109a013
• 作为产物：
  描述：

  氯甲基甲基醚 、 (+/-)-(1R*,6S*,8R*,9S*,11S*)-6-Methyl-2-methylene-12-oxatricyclo<6.3.1.0^1,6>dodecane-9,11-diol 在 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 42.0h， 以97%的产率得到(+/-)-(1R*,6S*,8R*,9S*,11S*)-9,11-Bis(methoxymethoxy)-6-methyl-2-methylene-12-oxatricyclo<6.3.1.0^1,6>dodecane
  参考文献：
  名称：

  Functionalization and Utility of Bridging Ethers in the Transformations of Bicyclo[5.4.0]undecanes

  摘要：

  Studies detail the formation and utility of bridged ethers of bicyclo[5.4.0]undecanes as a means for stereocontrolled functionalization as described in a survey of conjugate additions, reductions, and oxidative cyclizations. The intramolecular dipolar cycloaddition of 3-oxidopyrylium ylides affords a facile preparation of the starting trans-fused bicyclo[5.4.0]undecenone 1. Efficient methods toward highly oxygenated bicycloundecanes are described via the highly selective reductive cleavage of 12-oxatricyclo[6.3.1.0(1,6)]dodecanes such as 20 and 21. Reclosure of the era-bridge was examined. Vanadium-catalyzed oxidative reclosure of 24 led exclusively to the novel 2-oxatricyclo[5.4.1.0(3,8)]dodecane system 31.

  DOI：

  10.1021/jo00109a013