(+/-)-methyl [(3-endo)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene]-3-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 [(3-endo)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene]-3-carboxylate
• 英文别名: (+/-)-methyl 2-hydroxy-2-azabicyclo[2.2.1]-hept-5-ene-3-endo-carboxylate；(+/-)-methyl 2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene-3-endo-carboxylate；methyl (1S,3R,4R)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate
• 化学式: C₈H₁₁NO₃
• 分子量: 169.18
• InChiKey: BVNRHFPKRKXNJH-RRKCRQDMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  methyl 2-(hydroxyimino)acetate 、 环戊二烯 在 三氟化硼 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 生成 (+/-)-methyl [(3-endo)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene]-3-carboxylate 、 (+/-)-methyl (1R,4R,5R)-(2-oxa-3-azabicyclo[3.3.0]oct-7-ene)-4-carboxylate
  参考文献：
  名称：

  1,3- versus 1,4-[π4+π2] Cycloadditions between methyl glyoxylate oxime and cyclopentadiene or cyclopentene

  摘要：

  The acid catalyzed cycloaddition reaction of methyl glyoxylate oxime with cyclopentadiene (CPD) afforded the corresponding aza-Diels-Alder adducts, the endo and exo isomers of (+/-)-methyl 2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylates, and as the major product a 1,3-cycloadduct, methyl (1RS,4RS,5RS)-(2-oxa-3-azabicyclo[3.3.0]oct-7-ene)-4-carboxylate. The similar reaction using cyclopentene (CP) provided only the 1,3-cycloadduct methyl (1SR,4RS,5SR)-(2-oxa-3-azabicyclo[3.3.0]octane)4-carboxylate. The influence of various parameters on the reaction outcome was studied and, based on the results obtained, a mechanism for the formation of both 1,3- and 1,4-cycloadducts is proposed. The structure of all adducts was confirmed by NMR spectroscopic data and/or by X-ray crystallography. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.12.073

文献信息

• Acid-catalyzed aza-Diels–Alder versus 1,3-dipolar cycloadditions of methyl glyoxylate oxime with cyclopentadiene
  作者：Carlos A.D. Sousa、M. Luísa C. Vale、José E. Rodríguez-Borges、Xerardo Garcia-Mera、Jesús Rodríguez-Otero

  DOI：10.1016/j.tetlet.2008.07.110

  日期：2008.9

  The acid-catalyzed 1,4- and 1,3-cycloadditions between methyl glyoxylate oxime (1) and cyclopentadiene were investigated using various Lewis and/or Bronsted acids at different temperatures in dichloromethane as solvent. Besides the expected new adducts, (+/-)-methyl [(3-exo)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene]-3-carboxylate (2) and (+/-)-methyl [(3-endo)-2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene]-3-carboxylate (3), a third adduct, (+/-)-methyl (1R,4R,5R)-(2-oxa-3-azabicyclo[3.3.0]oct-7-ene)-4-carboxylate (4), whose formation can be explained by a 1,3-dipolar cycloaddition, was obtained. Yields and product ratios were found to be more dependent on the catalyst than on the temperature; these results and the stereochemistry of the adducts, confirmed by spectroscopic data (H-1 and C-13 NMR) and by X-ray crystallography, were used to analyze and propose a mechanistic explanation for both cycloadditions. (C) 2008 Elsevier Ltd. All rights reserved.
• 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。
• 1,3- versus 1,4-[π4+π2] Cycloadditions between methyl glyoxylate oxime and cyclopentadiene or cyclopentene
  作者：Carlos A.D. Sousa、M. Luísa C. Vale、Xerardo Garcia-Mera、José E. Rodríguez-Borges

  DOI：10.1016/j.tet.2011.12.073

  日期：2012.2

  The acid catalyzed cycloaddition reaction of methyl glyoxylate oxime with cyclopentadiene (CPD) afforded the corresponding aza-Diels-Alder adducts, the endo and exo isomers of (+/-)-methyl 2-hydroxy-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylates, and as the major product a 1,3-cycloadduct, methyl (1RS,4RS,5RS)-(2-oxa-3-azabicyclo[3.3.0]oct-7-ene)-4-carboxylate. The similar reaction using cyclopentene (CP) provided only the 1,3-cycloadduct methyl (1SR,4RS,5SR)-(2-oxa-3-azabicyclo[3.3.0]octane)4-carboxylate. The influence of various parameters on the reaction outcome was studied and, based on the results obtained, a mechanism for the formation of both 1,3- and 1,4-cycloadducts is proposed. The structure of all adducts was confirmed by NMR spectroscopic data and/or by X-ray crystallography. (C) 2011 Elsevier Ltd. All rights reserved.