1,2-ditosyloxy-3,5-diazido-1α,2α,3β,5β-cyclopentane | 89332-85-4

• 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: 1,2-ditosyloxy-3,5-diazido-1α,2α,3β,5β-cyclopentane
• CAS: 89332-85-4
• 化学式: C₁₉H₂₀N₆O₆S₂
• 分子量: 492.536
• InChiKey: MCXDZSNVVRVMDT-SEXKYXSUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.91
• 重原子数：
  33.0
• 可旋转键数：
  8.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  184.26
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  1,2-ditosyloxy-3,5-diazido-1α,2α,3β,5β-cyclopentane 在 lithium aluminium tetrahydride 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 3,7-dibenzoyl-1α,2α,4α,6α-3,7-diazatricyclo<4.1.0.0^2.4>heptane
  参考文献：
  名称：

  Double inversion of the secondary nitrogens incis-Diaziridinocyclopentane

  摘要：

  Abstract1α,2α,4α,6α,‐3,7‐Diazatricyclo[4.1.0.02,4]heptane (cis‐diaziridinocyclopentane) (1) has been prepared from the analogous cis‐diepoxycyclopentane. Ring opening of the diepoxide with sodium azide produced a pair of regioisomeric azido alcohols. Tosylation and treatment with lithium aluminum hydride produced 1. The dibenzoyl derivative possessed the di‐exo stereochemistry for the tertiary aziridine nitrogens. The 1H spectrum of 1 was temperature dependent. Both the CH and NH resonances underwent decoalescence as the temperature was lowered. Because the rate was independent of concentration, the mechanism is probably inversion of the secondary nitrogen, the first such example to occur by the interchange of two diastereotopic, secondary (NH) amine nitrogens within the same molecule. The free energy of activation at coalescence (0 °C) was measured to be 12.8 kcal mol−1. The unsymmetrical slow exchange of 1 is clearly consistent with the exo,endo stereochemistry for the secondary aziridine nitrogens, possibly stabilized by intramolecular attraction.

  DOI：

  10.1002/omr.1270211114
• 作为产物：
  描述：

  cis-1α,2α,4α,6α-3,7-dioxatricyclo<4.1.0.0^2,4>heptane 、 对甲苯磺酰氯 在 吡啶 、 sodium azide 作用下， 生成 1-tosyloxy-3,5-diazido-1α,2α,3β,5β-cyclopentan-2-ol 、 1,3-ditosyloxy-2,5-diazido-1α,2β,3α,5β-cyclopentane 、 1,2-ditosyloxy-3,5-diazido-1α,2α,3β,5β-cyclopentane
  参考文献：
  名称：

  Double inversion of the secondary nitrogens incis-Diaziridinocyclopentane

  摘要：

  Abstract1α,2α,4α,6α,‐3,7‐Diazatricyclo[4.1.0.02,4]heptane (cis‐diaziridinocyclopentane) (1) has been prepared from the analogous cis‐diepoxycyclopentane. Ring opening of the diepoxide with sodium azide produced a pair of regioisomeric azido alcohols. Tosylation and treatment with lithium aluminum hydride produced 1. The dibenzoyl derivative possessed the di‐exo stereochemistry for the tertiary aziridine nitrogens. The 1H spectrum of 1 was temperature dependent. Both the CH and NH resonances underwent decoalescence as the temperature was lowered. Because the rate was independent of concentration, the mechanism is probably inversion of the secondary nitrogen, the first such example to occur by the interchange of two diastereotopic, secondary (NH) amine nitrogens within the same molecule. The free energy of activation at coalescence (0 °C) was measured to be 12.8 kcal mol−1. The unsymmetrical slow exchange of 1 is clearly consistent with the exo,endo stereochemistry for the secondary aziridine nitrogens, possibly stabilized by intramolecular attraction.

  DOI：

  10.1002/omr.1270211114