methyl 2-oxo-1-phenylazetidine-3-carboxylate | 142612-63-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: methyl 2-oxo-1-phenylazetidine-3-carboxylate
• 英文别名: 3-carbomethoxy-1-phenyl-2-azetidinone
• CAS: 142612-63-3
• 化学式: C₁₁H₁₁NO₃
• 分子量: 205.213
• InChiKey: DTMWGBBOVSDOKW-UHFFFAOYSA-N

物化性质

• 沸点：
  394.5±35.0 °C(Predicted)
• 密度：
  1.279±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  N-苯基香豆甲酯 在 dirhodium tetraacetate 吡啶 、 氢氧化钾 、 四丁基碘化铵 、 sodium hydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 甲烷磺酰基叠氮化物 、 肼 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 methyl 2-oxo-1-phenylazetidine-3-carboxylate
  参考文献：
  名称：

  Dirhodium tetraacetate catalyzed carbon-hydrogen insertion reaction in N-substituted .alpha.-carbomethoxy-.alpha.-diazoacetanilides and structural analogs. Substituent and conformational effects

  摘要：

  A series of acyclic alpha-carbomethoxy-alpha-diazoacetanilides with different N-substituents, 5a-k, was prepared and the rhodium(II) acetate catalyzed reactions studied. It was found that the rhodium carbenoid reaction with these compounds occurred only at the N-substituent; when the N-substituent is a propargyl group, rhodium carbenoid addition to the triple bond is favored, resulting, ultimately, in the formation of a bicyclic furan derivative 8. With an N-(tert-butyloxycarbonyl)methyl substituent, interception of the rhodium carbenoid by the ester carbonyl oxygen occurred preferentially to give, eventually, 1,4-oxazine derivatives 9 and 9'. For N-alkyl substituents, rhodium carbenoid carbon-hydrogen (C-H) insertion into the alkyl group to give 2-azetidinone and/or 2-pyrrolidinone derivatives was observed. The chemoselectivity of the rhodium carbenoid C-H insertion can be altered by the use of the alpha-acetyl and alpha-phenylsulfonyl substituents. In these cases, exclusive C-H insertion at the N-aryl moiety resulted to give 2(3H)-indolinone products. However, the alpha-substituent effect on the chemoselectivity of the insertion reaction is easily overridden by conformational effects about the amide N-C(O) bond as revealed by the insertion reactions of the conformationally rigid compounds 20a-c. The alpha-substituent effects are reestablished when conformational rigidity is removed, as exemplified by the rhodium carbenoid insertion reactions of compounds 29a,b.

  DOI：

  10.1021/jo00042a018

文献信息

• Palladium-catalysed intramolecular carbenoid insertion of α-diazo-α-(methoxycarbonyl)acetanilides for oxindole synthesis
  作者：Daniel Solé、Ferran Pérez-Janer、Israel Fernández

  DOI：10.1039/c7cc00718c

  日期：——

  A novel, selective palladium-catalysed carbenoid C(aryl)-H insertion of [small alpha]-diazo-[small alpha]-(methoxycarbonyl)acetanilides leading to oxindoles is described.

  描述了新颖的，选择性的钯催化的生成的小α-重氮-[小α]-（甲氧羰基）乙酰胺的钯催化类胡萝卜素C（芳基）-H插入。
• Dirhodium tetraacetate catalyzed carbon-hydrogen insertion reaction in N-substituted .alpha.-carbomethoxy-.alpha.-diazoacetanilides and structural analogs. Substituent and conformational effects
  作者：Andrew G. H. Wee、Baosheng Liu、Lin Zhang

  DOI：10.1021/jo00042a018

  日期：1992.7

  A series of acyclic alpha-carbomethoxy-alpha-diazoacetanilides with different N-substituents, 5a-k, was prepared and the rhodium(II) acetate catalyzed reactions studied. It was found that the rhodium carbenoid reaction with these compounds occurred only at the N-substituent; when the N-substituent is a propargyl group, rhodium carbenoid addition to the triple bond is favored, resulting, ultimately, in the formation of a bicyclic furan derivative 8. With an N-(tert-butyloxycarbonyl)methyl substituent, interception of the rhodium carbenoid by the ester carbonyl oxygen occurred preferentially to give, eventually, 1,4-oxazine derivatives 9 and 9'. For N-alkyl substituents, rhodium carbenoid carbon-hydrogen (C-H) insertion into the alkyl group to give 2-azetidinone and/or 2-pyrrolidinone derivatives was observed. The chemoselectivity of the rhodium carbenoid C-H insertion can be altered by the use of the alpha-acetyl and alpha-phenylsulfonyl substituents. In these cases, exclusive C-H insertion at the N-aryl moiety resulted to give 2(3H)-indolinone products. However, the alpha-substituent effect on the chemoselectivity of the insertion reaction is easily overridden by conformational effects about the amide N-C(O) bond as revealed by the insertion reactions of the conformationally rigid compounds 20a-c. The alpha-substituent effects are reestablished when conformational rigidity is removed, as exemplified by the rhodium carbenoid insertion reactions of compounds 29a,b.