(+/-)-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.