5,5,6,6-tetracyano-1,2,3,4-tetramethyl-7-thiabicyclo[2.2.1]hept-2-ene S-oxide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫杂环戊烷
• 英文名称: 5,5,6,6-tetracyano-1,2,3,4-tetramethyl-7-thiabicyclo[2.2.1]hept-2-ene S-oxide
• 英文别名: 1,4,5,6-Tetramethyl-7-oxo-7lambda4-thiabicyclo[2.2.1]hept-5-ene-2,2,3,3-tetracarbonitrile；1,4,5,6-tetramethyl-7-oxo-7λ4-thiabicyclo[2.2.1]hept-5-ene-2,2,3,3-tetracarbonitrile
• 化学式: C₁₄H₁₂N₄OS
• 分子量: 284.341
• InChiKey: GGRNOQGLRZEVJX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  131
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2,3,4,5-四甲基噻吩 、 四氰基乙烯 在 三氟化硼乙醚 、 间氯过氧苯甲酸 作用下， 生成 5,5,6,6-tetracyano-1,2,3,4-tetramethyl-7-thiabicyclo[2.2.1]hept-2-ene S-oxide
  参考文献：
  名称：

  Lewis Acid Catalysis in the Oxidative Cycloaddition of Thiophenes¹

  摘要：

  Thiophenes 1 were treated with m-chloroperbenzoic acid (m-CPBA) under BF3 . Et2O catalysis to afford thiophene S-monoxides. These could be reacted in situ as intermediary species with a number of dienophiles to provide arenes (with alkynes as dienophiles) or 7-thiabicyclo[2.2.1]hept-2-ene 7-oxides (with alkenes as dienophiles). It was also possible to isolate thiophene S-monoxides in solution and to cycloadd them in a second step. In either way it could be shown that the use of BF3 . Et2O enhances the yields of the oxidative cycloaddition of thiophenes considerably. Moreover a greater variety of dienophiles (29a, 29b, 29c) could be reacted with thiophenes than in the case of the noncatalyzed reaction. All cycloadditions catalyzed by BF3 . Et2O give only a single diastereoisomer as cycloadduct. The reactions show a high pi-facial selectivity, a fact that can be explained by the Cieplak-effect. Without added dienophiles, 2-methylthiophene (le) gave a single dimer (36) of 2-methylthiophene S-monoxide, whereas 2,5-dimethylthiophene (la) gave three dimers (32a-c). In the case of tetrasubstituted thiophenes, thiophene S-monoxides (e.g., 31b and 31c) could be isolated in substance.

  DOI：

  10.1021/jo961985z

文献信息

• Lewis Acid Catalysis in the Oxidative Cycloaddition of Thiophenes¹
  作者：Yuanqiang Li、Thies Thiemann、Tsuyoshi Sawada、Shuntaro Mataka、Masashi Tashiro

  DOI：10.1021/jo961985z

  日期：1997.11.1

  Thiophenes 1 were treated with m-chloroperbenzoic acid (m-CPBA) under BF3 . Et2O catalysis to afford thiophene S-monoxides. These could be reacted in situ as intermediary species with a number of dienophiles to provide arenes (with alkynes as dienophiles) or 7-thiabicyclo[2.2.1]hept-2-ene 7-oxides (with alkenes as dienophiles). It was also possible to isolate thiophene S-monoxides in solution and to cycloadd them in a second step. In either way it could be shown that the use of BF3 . Et2O enhances the yields of the oxidative cycloaddition of thiophenes considerably. Moreover a greater variety of dienophiles (29a, 29b, 29c) could be reacted with thiophenes than in the case of the noncatalyzed reaction. All cycloadditions catalyzed by BF3 . Et2O give only a single diastereoisomer as cycloadduct. The reactions show a high pi-facial selectivity, a fact that can be explained by the Cieplak-effect. Without added dienophiles, 2-methylthiophene (le) gave a single dimer (36) of 2-methylthiophene S-monoxide, whereas 2,5-dimethylthiophene (la) gave three dimers (32a-c). In the case of tetrasubstituted thiophenes, thiophene S-monoxides (e.g., 31b and 31c) could be isolated in substance.