(+/-)-methyl 2-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-endo-carboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (+/-)-methyl 2-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-endo-carboxylate
• 英文别名: (+/-)-methyl N-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-endo-carboxylate；methyl (1R,3S,4S)-2-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate
• 化学式: C₂₀H₂₀NO₄P
• 分子量: 369.357
• InChiKey: RRYIWCMDFTYHFS-GJYPPUQNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (+/-)-methyl 2-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-endo-carboxylate 在 四氧化锇 、 水 、 N-甲基吗啉氧化物 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 叔丁醇 为溶剂， 反应 1.0h， 生成 (+/-)-methyl 5,6-dihydroxy-N-diphenylphosphoryl-2-azabicyclo[2.2.1]heptane-3-endo-carboxylate
  参考文献：
  名称：

  Structural analysis of three methyl N-phosphorylated 5,6-dihydroxy-2-azabicyclo[2.2.1]heptane-3-carboxylates

  摘要：

  Both exo and endo isomers of (+/-)-methyl N-diphenylphosphoryl-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate and (+/-)-methyl N-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate were dihydroxylated with OsO4. The unexpected formation of (+/-)-methyl 5,6-dihydroxy-N-diphenylphosphoryl-2-azabicyclo[2.2.1]heptane-3-endo-carboxylate from (+/-)-methyl N-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-endo-carboxylate is discussed based on NMR analyses and experimental observations. The two N-diphenylphosphoryl dihydroxybicycles are analyzed in terms of their crystalline structure by X-ray crystallography. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2011.09.041
• 作为产物：
  描述：

  (+/-)-methyl [(3-endo)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene]-3-carboxylate 、 二苯基次膦酰氯 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以43%的产率得到(+/-)-methyl 2-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-endo-carboxylate
  参考文献：
  名称：

  Phosphorylation of 2-azabicyclo[2.2.1]hept-5-ene and 2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene systems: synthesis and mechanistic study

  摘要：

  (±)-甲基 2-羟基-2-氮杂双环[2.2.1]庚-5-烯-3-羧酸内、外异构体和原位制备的(±)-甲基 2-氮杂双环[2.2.1]庚-5-烯-3-羧酸甲酯的内向异构体和外向异构体用二苯基膦酰氯（OPClPh2）和氯二苯基膦（ClPPh2）处理，得到相应的磷酸化双环化合物。所有这些化合物的结构都已通过核磁共振光谱和质谱法明确确定，并根据所获得的结果，提出了这些加合物的磷酸化反应生成相应的磷酸化双环的机理方案。

  DOI：

  10.1039/c0nj00239a

文献信息

• Phosphorylation of 2-azabicyclo[2.2.1]hept-5-ene and 2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene systems: synthesis and mechanistic study
  作者：Carlos A. D. Sousa、M. Luísa C. Vale、José E. Rodríguez-Borges、Xerardo García-Mera

  DOI：10.1039/c0nj00239a

  日期：——

  The endo and exo isomers of (±)-methyl 2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylates and the in situ-prepared endo and exo isomers of (±)-methyl 2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate were treated with diphenylphosphinic chloride (OPClPh2) and chlorodiphenylphosphine (ClPPh2) to afford the corresponding phosphorylated bicycles. The structure of all these compounds was unequivocally determined by NMR spectroscopy and mass spectrometry, and, based on the results obtained, a mechanistic scheme for the phosphorylation reaction of these adducts to afford the corresponding phosphorylbicycles is proposed.

  (±)-甲基 2-羟基-2-氮杂双环[2.2.1]庚-5-烯-3-羧酸内、外异构体和原位制备的(±)-甲基 2-氮杂双环[2.2.1]庚-5-烯-3-羧酸甲酯的内向异构体和外向异构体用二苯基膦酰氯（OPClPh2）和氯二苯基膦（ClPPh2）处理，得到相应的磷酸化双环化合物。所有这些化合物的结构都已通过核磁共振光谱和质谱法明确确定，并根据所获得的结果，提出了这些加合物的磷酸化反应生成相应的磷酸化双环的机理方案。
• Structural analysis of three methyl N-phosphorylated 5,6-dihydroxy-2-azabicyclo[2.2.1]heptane-3-carboxylates
  作者：Carlos A.D. Sousa、M. Luísa C. Vale、José E. Rodríguez-Borges、Xerardo Garcia-Mera

  DOI：10.1016/j.molstruc.2011.09.041

  日期：2012.1

  Both exo and endo isomers of (+/-)-methyl N-diphenylphosphoryl-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate and (+/-)-methyl N-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate were dihydroxylated with OsO4. The unexpected formation of (+/-)-methyl 5,6-dihydroxy-N-diphenylphosphoryl-2-azabicyclo[2.2.1]heptane-3-endo-carboxylate from (+/-)-methyl N-diphenylphosphoryloxy-2-azabicyclo[2.2.1]hept-5-ene-3-endo-carboxylate is discussed based on NMR analyses and experimental observations. The two N-diphenylphosphoryl dihydroxybicycles are analyzed in terms of their crystalline structure by X-ray crystallography. (C) 2011 Elsevier B.V. All rights reserved.