trans-2-thiabicyclo<4.3.0>nonan-5α-ol 2,2-dioxide | 138331-46-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻烷
• 英文名称: trans-2-thiabicyclo<4.3.0>nonan-5α-ol 2,2-dioxide
• 英文别名: (4S,4aR,7aS)-1,1-dioxo-2,3,4,4a,5,6,7,7a-octahydrocyclopenta[b]thiopyran-4-ol
• CAS: 138331-46-1
• 化学式: C₈H₁₄O₃S
• 分子量: 190.263
• InChiKey: QHLQGECPJDNMAJ-CSMHCCOUSA-N

物化性质

• 沸点：
  410.4±38.0 °C(Predicted)
• 密度：
  1.318±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  12
• 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：
  62.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (E)-thiacyclonon-4-ene 1,1-dioxide 在 tetrabutylammonium fluoride absorbed on silica gel 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 生成 trans-2-thiabicyclo<4.3.0>nonan-5α-ol 2,2-dioxide
  参考文献：
  名称：

  Desilylative transannular cyclization of nine-membered .alpha.-silyl (E)-.gamma.-epoxy sulfones

  摘要：

  Anionic desilylation of alpha-silylated (E)-4,5-epoxythiacyclononane 1,1-dioxides results in formation of transannular cyclization products whose distribution is independent of the stereochemistry of the starting material. Unlike the species formed by direct BuLi metalation,1 the intermediate arising from the 9-sily regioisomer rapidly and indiscriminately attacks either epoxidic carbon forming both cis- and trans-joined bicyclic products. This lack of selectivity suggests the reactive intermediate is not a hypervalent silicon species, but is more likely a carbanion which, being associated to a large cation (K+ or Bu4N+) is less discriminating than that arising from BuLi metalation. The intermediate formed by desilylation of the 2-silyl regioisomer appears to cyclize relatively slowly, such that transfer of the carbanionic functionality from C-2 to C-9 becomes competitive with cyclization. With this substrate an unexpected phenomenon has emerged, namely that t-BuOK may act as a base or a desilylating agent depending on the temperature.

  DOI：

  10.1021/jo00031a024

文献信息

• Desilylative transannular cyclization of nine-membered .alpha.-silyl (E)-.gamma.-epoxy sulfones
  作者：Vanda Cere、Claudio Paolucci、Salvatore Pollicino、Edda Sandri、Antonino Fava

  DOI：10.1021/jo00031a024

  日期：1992.2

  Anionic desilylation of alpha-silylated (E)-4,5-epoxythiacyclononane 1,1-dioxides results in formation of transannular cyclization products whose distribution is independent of the stereochemistry of the starting material. Unlike the species formed by direct BuLi metalation,1 the intermediate arising from the 9-sily regioisomer rapidly and indiscriminately attacks either epoxidic carbon forming both cis- and trans-joined bicyclic products. This lack of selectivity suggests the reactive intermediate is not a hypervalent silicon species, but is more likely a carbanion which, being associated to a large cation (K+ or Bu4N+) is less discriminating than that arising from BuLi metalation. The intermediate formed by desilylation of the 2-silyl regioisomer appears to cyclize relatively slowly, such that transfer of the carbanionic functionality from C-2 to C-9 becomes competitive with cyclization. With this substrate an unexpected phenomenon has emerged, namely that t-BuOK may act as a base or a desilylating agent depending on the temperature.