2-二氮杂-3-(乙基(苯基)氨基)-3-氧代丙酸甲酯 | 142612-52-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-二氮杂-3-(乙基(苯基)氨基)-3-氧代丙酸甲酯
• 英文名称: N-ethyl-N-phenyl-α-(methoxycarbonyl)-α-diazoacetamide
• 英文别名: methyl 2-diazo-3-(N-ethylanilino)-3-oxopropanoate
• CAS: 142612-52-0
• 化学式: C₁₂H₁₃N₃O₃
• 分子量: 247.254
• InChiKey: VXLJZYHMSOVRMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  48.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-二氮杂-3-(乙基(苯基)氨基)-3-氧代丙酸甲酯 在 tris-(dibenzylideneacetone)dipalladium(0) 、 caesium carbonate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 96.0h， 以78%的产率得到methyl 3-(2-chloroethyl)-1-ethyl-2-oxoindoline-3-carboxylate
  参考文献：
  名称：

  α-重氮-α-（甲氧基羰基）乙酰胺的 Pd 催化反应中的位点选择性：催化剂和底物取代对羟吲哚和 β-内酰胺合成的影响

  摘要：

  研究了 Pd 催化的 α-重氮-α-（甲氧基羰基）乙酰胺的分子内卡宾 C-H 插入以制备羟吲哚和 β-内酰胺。为了确定哪些因素会影响过程的选择性，我们使用 Pd 的两种氧化态和各种配体，探索了催化剂类型如何影响反应。研究发现，在羟吲哚的合成中，((IMes)Pd(NQ))2 可以作为 Pd2(dba)3 的替代物来催化卡宾 CArsp2-H 插入，尽管它的通用性较差。另一方面，已经证明 Pd(0) 和 Pd(II) 催化剂都可以有效地促进 Csp3-H 插入导致 β-内酰胺，后者是最有效的。DFT 计算提供了对这些转换中涉及的反应机制的深入了解。

  DOI：

  10.3390/molecules24193551
• 作为产物：
  描述：

  N-苯基香豆甲酯 在 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， 反应 2.0h， 生成 2-二氮杂-3-(乙基(苯基)氨基)-3-氧代丙酸甲酯
  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。
• The Nafion-H Catalysed Cyclization of α-Carbomethoxy-α-Diazoacetanilides. Synthesis of 3-Unsubstituted-2-Indolinones.
  作者：Andrew G. Wee、Baosheng Liu

  DOI：10.1016/s0040-4020(01)80781-x

  日期：1994.1

  Diazoanilides of type 4 were found to undergo Nafion-H catalysed cyclization onto the aromatic ring and concomitant decarboxylation, under optimal conditions, to give 3-unsubstituted 2-indolinones 5 in moderate yields. Diazoanilides that possess electron-donating substituents in the aromatic moiety gave higher yields of 5 and, in one case, the presence of an electron-withdrawing group in the aromatic moiety did not impede the cyclization. In the case of the diazoanilides that possess a N-butenyl group, preferential 1,3-dipolar cycloaddition of the diazo unit onto the butenyl double bond occurred to give an unstable 1-pyrazoline which was converted, by loss of nitrogen accompanied by hydrogen migration, to dihydro-2-pyridinone derivatives. It was also found that substituents ortho to the amido group and/or the site of cyclization sterically retarded the cyclization.
• 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.
• Site Selectivity in Pd-Catalyzed Reactions of α-Diazo-α-(methoxycarbonyl)acetamides: Effects of Catalysts and Substrate Substitution in the Synthesis of Oxindoles and β-Lactams
  作者：Daniel Solé、Ferran Pérez-Janer、Arianna Amenta、M.-Lluïsa Bennasar、Israel Fernández

  DOI：10.3390/molecules24193551

  日期：——

  α-diazo-α-(methoxycarbonyl)acetamides to prepare oxindoles as well as β-lactams was studied. In order to identify what factors influence the selectivity of the processes, we explored how the reactions are affected by the catalyst type, using two oxidation states of Pd and a variety of ligands. It was found that, in the synthesis of oxindoles, ((IMes)Pd(NQ))2 can be used as an alternative to Pd2(dba)3

  研究了 Pd 催化的 α-重氮-α-（甲氧基羰基）乙酰胺的分子内卡宾 C-H 插入以制备羟吲哚和 β-内酰胺。为了确定哪些因素会影响过程的选择性，我们使用 Pd 的两种氧化态和各种配体，探索了催化剂类型如何影响反应。研究发现，在羟吲哚的合成中，((IMes)Pd(NQ))2 可以作为 Pd2(dba)3 的替代物来催化卡宾 CArsp2-H 插入，尽管它的通用性较差。另一方面，已经证明 Pd(0) 和 Pd(II) 催化剂都可以有效地促进 Csp3-H 插入导致 β-内酰胺，后者是最有效的。DFT 计算提供了对这些转换中涉及的反应机制的深入了解。