trans-3-carbomethoxy-1-(p-methoxyphenyl)-4-phenyl-2-pyrrolidinone | 142612-75-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: trans-3-carbomethoxy-1-(p-methoxyphenyl)-4-phenyl-2-pyrrolidinone
• 英文别名: methyl (3S,4R)-1-(4-methoxyphenyl)-2-oxo-4-phenylpyrrolidine-3-carboxylate
• CAS: 142612-75-7
• 化学式: C₁₉H₁₉NO₄
• 分子量: 325.364
• InChiKey: PWBALPNYMABJOV-IRXDYDNUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  N-(4-甲氧基苯基)氨基甲酸甲酯 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 4.5h， 生成 trans-3-carbomethoxy-1-(p-methoxyphenyl)-4-phenyl-2-pyrrolidinone
  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

• Enantioselective Synthesis of 4-Substituted 2-Pyrrolidinones by Site-selective C-H Insertion of α-Methoxycarbonyl-α-diazoacetanilides Catalyzed by Dirhodium(II) Tetrakis[N-phthaloyl-(S)-tert-leucinate]
  作者：Masahiro Anada、Shun-ichi Hashimoto

  DOI：10.1016/s0040-4039(97)10493-2

  日期：1998.1

  Site- and enantioselective intramolecular C-H insertion of alpha-methoxycarbonyl-alpha-diazoacetamides has been achieved by exploiting a p-nitrophenyl group as the N-substituent and dirhodium(ll) tetrakis[N-phthaloyl-(S)-tert-leucinate] as catalyst, leading to the formation of 4-substituted 2-pyrrolidinone derivatives of up to 82% ee. The efficiency of the present protocol has been verified well by a short-step synthesis of(R)-(-)-baclofen. (C) 1997 Elsevier Science Ltd. All rights reserved.
• 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.