cis-7-thiabicyclo<4.3.0>nonan-2-one ethylene ketal | 134333-96-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-7-thiabicyclo<4.3.0>nonan-2-one ethylene ketal
• CAS: 134333-96-3
• 化学式: C₁₀H₁₆O₂S
• 分子量: 200.302
• InChiKey: KUNWSKLISIIOCS-RKDXNWHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.04
• 重原子数：
  13.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  cis-7-thiabicyclo<4.3.0>nonan-2-one ethylene ketal 在 硫酸 作用下， 以 丙酮 为溶剂， 反应 1.0h， 以100%的产率得到(3aR,7aS)-Hexahydro-benzo[b]thiophen-4-one
  参考文献：
  名称：

  Medium-ring .gamma.-epoxy sulfones. Regio- and stereochemistry of the butyllithium-promoted transannular epoxide ring opening

  摘要：

  Cyclic 8- and 9-membered E and Z gamma-epoxy sulfones yield bicyclic hydroxy sulfones stereospecifically upon treatment with BuLi in THF. The distribution of regioisomeric products markedly depends on the metalation mode, portionwise or at once. This suggests that the metal/proton exchange between the two positions alpha to the sulfone function is slow, relative to transannular cyclization, under conditions of complete metalation, but becomes fast in the presence of unmetalated sulfone (probably acting as a H+-transfer agent). The product distribution also depends, though to a lesser extent, on temperature, perhaps in relation to changes in the aggregation of the organolithium intermediate. An unexpected phenomenon was observed with the 8-membered Z epoxy sulfone at -70-degrees-C, where the time dependence of the transannular cyclization is consistent with an equilibrium being reached at 2/3 conversion. However, at -40-degrees-C or higher the reaction proceeds to completion without difficulty. A low-temperature metastable equilibrium is suggested involving some kind of aggregate of the lithio sulfone with the lithioalkoxide product.

  DOI：

  10.1021/jo00014a035
• 作为产物：
  描述：

  (7-Oxo-1,4-dioxa-spiro[4.5]dec-6-yl)-acetic acid 在 sodium sulfide 、 lithium aluminium tetrahydride 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 cis-7-thiabicyclo<4.3.0>nonan-2-one ethylene ketal
  参考文献：
  名称：

  Medium-ring .gamma.-epoxy sulfones. Regio- and stereochemistry of the butyllithium-promoted transannular epoxide ring opening

  摘要：

  Cyclic 8- and 9-membered E and Z gamma-epoxy sulfones yield bicyclic hydroxy sulfones stereospecifically upon treatment with BuLi in THF. The distribution of regioisomeric products markedly depends on the metalation mode, portionwise or at once. This suggests that the metal/proton exchange between the two positions alpha to the sulfone function is slow, relative to transannular cyclization, under conditions of complete metalation, but becomes fast in the presence of unmetalated sulfone (probably acting as a H+-transfer agent). The product distribution also depends, though to a lesser extent, on temperature, perhaps in relation to changes in the aggregation of the organolithium intermediate. An unexpected phenomenon was observed with the 8-membered Z epoxy sulfone at -70-degrees-C, where the time dependence of the transannular cyclization is consistent with an equilibrium being reached at 2/3 conversion. However, at -40-degrees-C or higher the reaction proceeds to completion without difficulty. A low-temperature metastable equilibrium is suggested involving some kind of aggregate of the lithio sulfone with the lithioalkoxide product.

  DOI：

  10.1021/jo00014a035