2-(5-chloro-2-triphenylphosphoranylideneaminophenyl)-1,3-oxathiane | 1376758-78-9

• 英文名称: 2-(5-chloro-2-triphenylphosphoranylideneaminophenyl)-1,3-oxathiane
• 英文别名: [4-Chloro-2-(1,3-oxathian-2-yl)phenyl]imino-triphenyl-lambda5-phosphane；[4-chloro-2-(1,3-oxathian-2-yl)phenyl]imino-triphenyl-λ5-phosphane
• CAS: 1376758-78-9
• 化学式: C₂₈H₂₅ClNOPS
• 分子量: 490.005
• InChiKey: ZSQFWUJAGKOYLQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  33
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  46.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(5-chloro-2-triphenylphosphoranylideneaminophenyl)-1,3-oxathiane 、 二苯乙烯酮 以 邻二甲苯 为溶剂， 反应 12.5h， 生成 6'-chloro-3',3'-diphenylspiro[1,3-oxathiane-2,4'(3'H)quinoline]
  参考文献：
  名称：

  Tandem [1,5]-H shift/6π-electrocyclizations of ketenimines bearing 1,3-oxathiane units. Computational assessment of the experimental diastereoselection

  摘要：

  N-Aryl ketenimines bearing a 1,3-oxathiane function at the ortho position of the keteniminic nitrogen atom convert into spiro[1,3-oxathiane-2,4'(3'H)quinolines] under mild thermal treatment. These cyclization processes are interpreted in terms of a two-step tandem sequence involving a [1,5]-H migration followed by a 6 pi-electrocyclic ring closure. Moreover, the cyclization of 1,3-oxathiane-ketenimines having two different substituents at the terminal carbon atom of the ketenimine moiety provided spiroquinolines bearing two stereocenters, the C3 and C4 atoms, with moderate diastereoselectivity. A DFT study support that the mechanism of these conversions consists of a [1,5]-H shift/6 pi-electrocyclization sequence, in which the [1,5]-H shift is the rate-limiting step. A quantitative kinetic analysis of the cyclization of an oxathiane-ketenimine with a prochiral ketenimine function explains the sense and degree of the experimentally observed diastereoselectivity. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.04.021
• 作为产物：
  描述：

  2-azido-5-chlorobenzaldehyde 在 对甲苯磺酸 作用下， 以 乙醚 、 苯 为溶剂， 反应 15.0h， 生成 2-(5-chloro-2-triphenylphosphoranylideneaminophenyl)-1,3-oxathiane
  参考文献：
  名称：

  Tandem [1,5]-H shift/6π-electrocyclizations of ketenimines bearing 1,3-oxathiane units. Computational assessment of the experimental diastereoselection

  摘要：

  N-Aryl ketenimines bearing a 1,3-oxathiane function at the ortho position of the keteniminic nitrogen atom convert into spiro[1,3-oxathiane-2,4'(3'H)quinolines] under mild thermal treatment. These cyclization processes are interpreted in terms of a two-step tandem sequence involving a [1,5]-H migration followed by a 6 pi-electrocyclic ring closure. Moreover, the cyclization of 1,3-oxathiane-ketenimines having two different substituents at the terminal carbon atom of the ketenimine moiety provided spiroquinolines bearing two stereocenters, the C3 and C4 atoms, with moderate diastereoselectivity. A DFT study support that the mechanism of these conversions consists of a [1,5]-H shift/6 pi-electrocyclization sequence, in which the [1,5]-H shift is the rate-limiting step. A quantitative kinetic analysis of the cyclization of an oxathiane-ketenimine with a prochiral ketenimine function explains the sense and degree of the experimentally observed diastereoselectivity. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.04.021