N-acetyl-2-diazo-N-tert-butoxycarbonylmethyl-malonamic acid methyl ester | 192758-56-8

• 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: N-acetyl-2-diazo-N-tert-butoxycarbonylmethyl-malonamic acid methyl ester
• CAS: 192758-56-8
• 化学式: C₁₂H₁₇N₃O₆
• 分子量: 299.283
• InChiKey: SXQWRAXEYSAWCH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.45
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  126.38
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  N-苯基马来酰亚胺 、 N-acetyl-2-diazo-N-tert-butoxycarbonylmethyl-malonamic acid methyl ester 在 rhodium(II) perfluorobutyroamidate 作用下， 以 苯 为溶剂， 以66%的产率得到8-tert-butoxycarbonylmethyl-7-methyl-3,5,9-trioxo-4-phenyl-10-oxa-8-azatricyclo[5.2.1.0^2,6]decane-1-carboxylic acid methyl ester
  参考文献：
  名称：

  Site selectivity in the rhodium(II)-catalyzed reaction of α-diazoimides. Ligand and substituent effects

  摘要：

  The product distribution obtained from Rh(II)-catalyzed decomposition of alpha-diazoimides derived from glycine methyl ester has been found to be selectively controlled by the proper choice of catalyst. When the reaction was carried out using perfluorinated ligands, the diazoimide cyclized to produce an isomunchnone dipole whose formation could be monitored by NMR spectroscopy. Reaction of the dipole with a trapping agent such as N-phenylmaleimide resulted in the isolation of a 1,3-dipolar cycloadduct in high yield. The product distribution changed dramatically when rhodium(II)-acetate was employed as the catalyst. The products obtained from this reaction were derived from an azabicyclic epoxide intermediate. The catalyst effect can be modulated by the addition of Sc(OTf)(3) as a Lewis acid or by using nitromethane as the solvent. Changing the nature of the interacting carbonyl group had little effect on the cyclization pathways. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00479-1
• 作为产物：
  描述：

  N-acetyl glycine tert-butyl ester 在 p-nitrobenzenesulfonyl azide 、 三乙胺 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 10.0h， 生成 N-acetyl-2-diazo-N-tert-butoxycarbonylmethyl-malonamic acid methyl ester
  参考文献：
  名称：

  Site selectivity in the rhodium(II)-catalyzed reaction of α-diazoimides. Ligand and substituent effects

  摘要：

  The product distribution obtained from Rh(II)-catalyzed decomposition of alpha-diazoimides derived from glycine methyl ester has been found to be selectively controlled by the proper choice of catalyst. When the reaction was carried out using perfluorinated ligands, the diazoimide cyclized to produce an isomunchnone dipole whose formation could be monitored by NMR spectroscopy. Reaction of the dipole with a trapping agent such as N-phenylmaleimide resulted in the isolation of a 1,3-dipolar cycloadduct in high yield. The product distribution changed dramatically when rhodium(II)-acetate was employed as the catalyst. The products obtained from this reaction were derived from an azabicyclic epoxide intermediate. The catalyst effect can be modulated by the addition of Sc(OTf)(3) as a Lewis acid or by using nitromethane as the solvent. Changing the nature of the interacting carbonyl group had little effect on the cyclization pathways. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00479-1