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.