(E)-thiacyclonon-4-ene 1,1-dioxide | 79760-37-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 磺酰类
• 英文名称: (E)-thiacyclonon-4-ene 1,1-dioxide
• 英文别名: (6E)-2,3,4,5,8,9-hexahydrothionine 1,1-dioxide
• CAS: 79760-37-5
• 化学式: C₈H₁₄O₂S
• 分子量: 174.264
• InChiKey: KUZSPVVDWZLMDH-HNQUOIGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  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 cis-2-thiabicyclo<4.3.0>nonan-5β-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
• 作为产物：
  描述：

  (E)-thiacyclonon-4-ene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以91%的产率得到(E)-thiacyclonon-4-ene 1,1-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

• Stereospecific intramolecular addition of α-lithio sulphoxides or sulphones to inactivated double bonds
  作者：Vanda Ceré、Claudio Paolucci、Salvatore Pollicino、Edda Sandri、Antonino Fava

  DOI：10.1039/c39810000764

  日期：——

  Treatment of the l-oxides or l,l-dioxides of trans homoallylic 8–10 membered ring cyclic sulphides with BuLi in tetrahydrofuran result in transsnnular addition of the α-thio carbanion to the E double bond with formation of bicyclic products.

  在四氢呋喃中用BuLi处理反式均烯丙基8-10元环硫化物的l-氧化物或l，l-二氧化物会导致α-硫代碳负离子向环状双环加成至E双键并形成双环产物。
• CERE V.; PAOLUCCI C.; POLLICINO S.; SANDRI E.; FAVA A., J. CHEM. SOC. CHEM. COMMUN., 1981, NO 15, 764-765
  作者：CERE V.、 PAOLUCCI C.、 POLLICINO S.、 SANDRI E.、 FAVA A.

  DOI：——

  日期：——
• 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.

表征谱图