N-ethoxycarbonyl-3-anti-methyl-2-azabicyclo<2.2.2>octan-5-one | 83681-60-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: N-ethoxycarbonyl-3-anti-methyl-2-azabicyclo<2.2.2>octan-5-one
• 英文别名: N-carbethoxy-2-aza-3-exo-methylbicyclo<2.2.2>octan-5-one；ethyl (1S,3R,4S)-3-methyl-5-oxo-2-azabicyclo[2.2.2]octane-2-carboxylate
• CAS: 83681-60-1
• 化学式: C₁₁H₁₇NO₃
• 分子量: 211.261
• InChiKey: YYZNZKCZUAHKQO-VGMNWLOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-ethoxycarbonyl-3-anti-methyl-2-azabicyclo<2.2.2>octan-5-one 在 hydroxylamine-O-sulfonic acid 作用下， 以 甲酸 为溶剂， 反应 3.0h， 以93%的产率得到6-ethoxycarbonyl-7-anti-methyl-2,6-diazabicyclo<3.2.2>nonan-3-one
  参考文献：
  名称：

  Regioselective Functionalization. 7.¹ Unexpected Preferences for Bridgehead Migration in Schmidt Rearrangement Syntheses of Novel 2,6-Diazabicyclo[3.2.x]alkan-3-ones (x = 1−3)

  摘要：

  Regioselective syntheses of 2,6-diazabicyclo[3.2.x]alkan-3-ones (x = 1-3) 34 by insertion of nitrogen next to the bridgehead (BH) of 2-azabicyclo[2.2.x]alkanones 32 with hydroxylamine-O-sulfonic acid are described. The ketones 32 under Schmidt reaction conditions (HN3/H2SO4) afford major amounts of BK migrated lactams 34 but also, when x = 2 or 3, the methylene (IM) migrated lactams, 3,6-diazabicycl[3.2.x]alkan-2-ones 37. The present N-insertion reactions favoring BH migration with azabicyclic ketones contrast markedly with reactions of the related carbocycles la,b, which give only methylene migrated lactams 2a,b with HN3/H2SO4. Schmidt reactions of 3-anti/syn-methyl- and 3-anti-phenyl-2-azabicyclo[2.2.2]octan-5-ones 17, 20, and 23 (64:36 +/- 9, BH:M) follow the reaction pattern of the parent ketone 14, but the S-syn-phenyl ketone 26 gives major (65%) methylene migration. The results offer insights into the BH vs M migration dichotomy for the Beckmann and Schmidt reactions of bridged bicyclic ketones.

  DOI：

  10.1021/jo981977d

文献信息

• Regioselective functionalization. .beta. Substituent effects on the regioselectivity of Baeyer-Villiger oxidations of 3-substituted 2-azabicyclo[2.2.2]octan-5-ones (isoquinuclidin-5-ones)
  作者：Grant R. Krow、Constance A. Johnson、James P. Guare、Dennis Kubrak、Kenneth J. Henz、Donald A. Shaw、Steven W. Szczepanski、James T. Carey

  DOI：10.1021/jo00148a002

  日期：1982.12