1α,3β,5α,6α-3,6-dimorpholino-bicyclo[3.1.0]hexane-6-carbonitrile | 172587-00-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• 英文名称: 1α,3β,5α,6α-3,6-dimorpholino-bicyclo[3.1.0]hexane-6-carbonitrile
• CAS: 172587-00-7
• 化学式: C₁₅H₂₃N₃O₂
• 分子量: 277.367
• InChiKey: VASYJQBSLDPQND-BIQWYFBQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.32
• 重原子数：
  20.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  48.73
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  1α,3β,5α,6α-3,6-dimorpholino-bicyclo[3.1.0]hexane-6-carbonitrile 在 氨 、 sodium 作用下， 以82%的产率得到4,4'-(1α,3β,5α,6α-bicyclo[3.1.0]hexane-3,6-diyl)-dimorpholine
  参考文献：
  名称：

  Reductive Decyanation of Annulated Aminocyclopropane-endo-carbonitriles - a way to annulated cyclopropane-exo-amines

  摘要：

  Annulated Aminocyclopropane-endo-carbonitriles 11a,b are reductively decyanated by sodium in liquid ammonia with complete retention of configuration. An additionally existing chlorine atom in the starting materials 12a,c-e, thereby, is simultaneously replaced by hydrogen. The preparative advantage of this method is demonstrated by the selective access to 6 alpha-H-isomers 13b and 13e as members of the ensemble of bicyclo[3.1.0]hexanediyl-dimorpholine diastereomers. A strong buckled bicyclohexane unit is present in 3 alpha,6 alpha-isomer 13e as indicated by H-1 NMR spectroscopy and X-ray structural analysis.

  DOI：

  10.1002/prac.19983400410
• 作为产物：
  描述：

  4-(7,9-dichloro-1,4-dioxaspiro<4.5>dec-7-en-8-yl)-morpholine 在 titanium(IV) isopropylate 、 盐酸 、 sodium 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 水 、 叔丁醇 为溶剂， 反应 102.0h， 生成 1α,3β,5α,6α-3,6-dimorpholino-bicyclo[3.1.0]hexane-6-carbonitrile
  参考文献：
  名称：

  The ensemble of 3,6-diaminobicyclo[3.1.0]hexanecarbonitrile diastereomers — Constrained analogues of conformers of cyclohexane-1,4-diamine species

  摘要：

  Dimorpholinobicyclo[3.1.0]hexanecarbonitrile diastereomers la and 8a have been synthesized with high stereoselectivity starting from dichloroenamines 11 and 13. The sequence 11 --> 17 --> 19 and reductive amination of the latter provided isomer la. Ring closure of 13 by cyanide and subsequent dechlorination of 14 produced compound 8a. The stereochemistry of the cyclopropane forming reaction was studied using cis and trans isomers of chloroenamine 12: trans 12-t gave almost exclusively 3 alpha-morpholine derivatives 4a / 8a upon interaction of cyanide. Cis 12-c led to 3 alpha- and 3 beta-morpholine products 4a / 8a and 1a / 5a in a ratio of 3:1 indicating an aminoallylcation intermediate 30 in the former case. Cis-configuration of chloroenamine isomer 12-c was established by X-ray structural analysis.

  DOI：

  10.1016/0040-4020(95)00682-x