4-(methylseleno)-15-(p-toluenesulfonyl)<2.2>paracyclophane | 135562-16-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-(methylseleno)-15-(p-toluenesulfonyl)<2.2>paracyclophane
• 英文别名: 5-(4-Methylphenyl)sulfonyl-12-methylselanyltricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaene
• CAS: 135562-16-2
• 化学式: C₂₄H₂₄O₂SSe
• 分子量: 455.479
• InChiKey: DCUDNJAKOUHRKQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.09
• 重原子数：
  28
• 可旋转键数：
  3
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  4-(methylseleno)-15-(p-toluenesulfonyl)<2.2>paracyclophane 在 间氯过氧苯甲酸 作用下， 以 氘代氯仿 为溶剂， 反应 0.05h， 生成 、
  参考文献：
  名称：

  Asymmetric induction in the oxidation of [2.2]paracyclophane-substituted selenides. Application of chirality transfer in the selenoxide [2,3] sigmatropic rearrangement

  摘要：

  When selenides derived from [2.2]paracyclophane systems were oxidized, the chiral aryl substituent provided for asymmetric induction to the new selenoxide chiral center. The ratio of diastereomeric selenoxides obtained depended upon whether the oxidation was performed under kinetic conditions or whether the selenoxides were allowed to equilibrate. Thus 4-(methylseleno)[2.2]paracyclophane (10) gave a 1:1 kinetic ratio of selenoxides 11 and 12 on oxidation with m-chloroperbenzoic acid and a 30:1 ratio at equilibrium (thermodynamic ratio). The more hindered 4-(methylseleno)-15-(p-toluenesulfonyl)[2.2]paracyclophane (23) was prepared in almost optically pure form. It gave a better kinetic ratio of selenoxides 24 and 25 (4.5:1) but a poorer thermodynamic one (1.5:1). The relative configuration of 11 and 12 and the absolute configuration of 24 and 25 were assigned. A geranyl selenide substituted with a resolved [2.2]paracyclophane substituent was oxidized and allowed to undergo a selenoxide [2,3] sigmatropic rearrangement to linalool. This sequence proves that the [2,3] sigmatropic rearrangement of gamma,gamma-dialkylallyl selenoxides proceeds through an endo transition state and illustrates the use of asymmetric induction during oxidation followed by chirality transfer by rearrangement to prepare optically active allylic alcohols.

  DOI：

  10.1021/jo00019a039
• 作为产物：
  描述：

  (+/-)-4-(p-tolylthio)<2.2>paracyclophane 在 sodium tetrahydroborate 作用下， 反应 0.67h， 生成 4-(methylseleno)-15-(p-toluenesulfonyl)<2.2>paracyclophane
  参考文献：
  名称：

  Asymmetric induction in the oxidation of [2.2]paracyclophane-substituted selenides. Application of chirality transfer in the selenoxide [2,3] sigmatropic rearrangement

  摘要：

  When selenides derived from [2.2]paracyclophane systems were oxidized, the chiral aryl substituent provided for asymmetric induction to the new selenoxide chiral center. The ratio of diastereomeric selenoxides obtained depended upon whether the oxidation was performed under kinetic conditions or whether the selenoxides were allowed to equilibrate. Thus 4-(methylseleno)[2.2]paracyclophane (10) gave a 1:1 kinetic ratio of selenoxides 11 and 12 on oxidation with m-chloroperbenzoic acid and a 30:1 ratio at equilibrium (thermodynamic ratio). The more hindered 4-(methylseleno)-15-(p-toluenesulfonyl)[2.2]paracyclophane (23) was prepared in almost optically pure form. It gave a better kinetic ratio of selenoxides 24 and 25 (4.5:1) but a poorer thermodynamic one (1.5:1). The relative configuration of 11 and 12 and the absolute configuration of 24 and 25 were assigned. A geranyl selenide substituted with a resolved [2.2]paracyclophane substituent was oxidized and allowed to undergo a selenoxide [2,3] sigmatropic rearrangement to linalool. This sequence proves that the [2,3] sigmatropic rearrangement of gamma,gamma-dialkylallyl selenoxides proceeds through an endo transition state and illustrates the use of asymmetric induction during oxidation followed by chirality transfer by rearrangement to prepare optically active allylic alcohols.

  DOI：

  10.1021/jo00019a039

文献信息

• Asymmetric induction in the oxidation of [2.2]paracyclophane-substituted selenides. Application of chirality transfer in the selenoxide [2,3] sigmatropic rearrangement
  作者：Hans J. Reich、Kenneth E. Yelm

  DOI：10.1021/jo00019a039

  日期：1991.9

  When selenides derived from [2.2]paracyclophane systems were oxidized, the chiral aryl substituent provided for asymmetric induction to the new selenoxide chiral center. The ratio of diastereomeric selenoxides obtained depended upon whether the oxidation was performed under kinetic conditions or whether the selenoxides were allowed to equilibrate. Thus 4-(methylseleno)[2.2]paracyclophane (10) gave a 1:1 kinetic ratio of selenoxides 11 and 12 on oxidation with m-chloroperbenzoic acid and a 30:1 ratio at equilibrium (thermodynamic ratio). The more hindered 4-(methylseleno)-15-(p-toluenesulfonyl)[2.2]paracyclophane (23) was prepared in almost optically pure form. It gave a better kinetic ratio of selenoxides 24 and 25 (4.5:1) but a poorer thermodynamic one (1.5:1). The relative configuration of 11 and 12 and the absolute configuration of 24 and 25 were assigned. A geranyl selenide substituted with a resolved [2.2]paracyclophane substituent was oxidized and allowed to undergo a selenoxide [2,3] sigmatropic rearrangement to linalool. This sequence proves that the [2,3] sigmatropic rearrangement of gamma,gamma-dialkylallyl selenoxides proceeds through an endo transition state and illustrates the use of asymmetric induction during oxidation followed by chirality transfer by rearrangement to prepare optically active allylic alcohols.