ethyl 2-[(E)-2-chloro-3-methoxy-3-oxo-1-phenylprop-1-enylimino]-3-oxobutanoate | 1403871-55-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: ethyl 2-[(E)-2-chloro-3-methoxy-3-oxo-1-phenylprop-1-enylimino]-3-oxobutanoate
• 英文别名: ethyl 2-[(E)-2-chloro-3-methoxy-3-oxo-1-phenylprop-1-enyl]imino-3-oxobutanoate
• CAS: 1403871-55-5
• 化学式: C₁₆H₁₆ClNO₅
• 分子量: 337.76
• InChiKey: DXFKXFGXDDGCMH-JLNDKSMGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  82
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 2-[(E)-2-chloro-3-methoxy-3-oxo-1-phenylprop-1-enylimino]-3-oxobutanoate 以 甲苯 为溶剂， 反应 3.0h， 以19%的产率得到2-ethyl 3-methyl 2-acetyl-3-chloro-4-phenyl-2,3-dihydroazete-2,3-dicarboxylate
  参考文献：
  名称：

  4-Halo-2-azabuta-1,3-dienes as intermediates in the rhodium carbenoid-initiated transformation of 2-halo-2H-azirines into 2,3-dihydroazetes and 2,5-dihydrooxazoles

  摘要：

  A wide range of electron-poor 4-bromo-/4-chloro-2-azabuta-1,3-dienes were synthesized by the Rh-2(OAc)(4)-catalyzed reaction of diazo esters and diazo ketones with methyl 2-halo-2H-azirine-2-carboxylates. The E stereoselectivity with respect to the configuration of the C=C bond of the 2-azadiene moiety is in good agreement with the results of DFT (M06-2X/6-31+G(d,p)) calculations of the reaction pathway. The reaction proceeds via the formation of an azirinium ylide intermediate followed by ring opening with outward rotation of the halogen atom. Depending on the substitution pattern at C-1 electron-poor 4-halo-2-azabutadienes can undergo two types of cyclization at elevated temperatures: reversible 1,4-electrocyclization to give 2,3-dihydroazetes or 1,5-exo-trig cyclization to give 5-methylene-2,5-dihydrooxazoles, both in good yields. The dihydrooxazole derivatives can be also obtained at ambient temperature under DBU catalysis. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.05.022
• 作为产物：
  描述：

  重氮基乙酰乙酸乙酯 、 azirine 在 dirhodium tetraacetate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.01h， 以77%的产率得到ethyl 2-[(E)-2-chloro-3-methoxy-3-oxo-1-phenylprop-1-enylimino]-3-oxobutanoate
  参考文献：
  名称：

  4-Halo-2-azabuta-1,3-dienes as intermediates in the rhodium carbenoid-initiated transformation of 2-halo-2H-azirines into 2,3-dihydroazetes and 2,5-dihydrooxazoles

  摘要：

  A wide range of electron-poor 4-bromo-/4-chloro-2-azabuta-1,3-dienes were synthesized by the Rh-2(OAc)(4)-catalyzed reaction of diazo esters and diazo ketones with methyl 2-halo-2H-azirine-2-carboxylates. The E stereoselectivity with respect to the configuration of the C=C bond of the 2-azadiene moiety is in good agreement with the results of DFT (M06-2X/6-31+G(d,p)) calculations of the reaction pathway. The reaction proceeds via the formation of an azirinium ylide intermediate followed by ring opening with outward rotation of the halogen atom. Depending on the substitution pattern at C-1 electron-poor 4-halo-2-azabutadienes can undergo two types of cyclization at elevated temperatures: reversible 1,4-electrocyclization to give 2,3-dihydroazetes or 1,5-exo-trig cyclization to give 5-methylene-2,5-dihydrooxazoles, both in good yields. The dihydrooxazole derivatives can be also obtained at ambient temperature under DBU catalysis. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.05.022

文献信息

• Synthesis of electron-poor 4-halo-2-azabuta-1,3-dienes by Rh(II)-catalyzed diazo ester–azirine coupling. 2-Azabuta-1,3-diene-2,3-dihydroazete valence isomerism
  作者：Mikhail S. Novikov、Ilia A. Smetanin、Alexander F. Khlebnikov、Nikolai V. Rostovskii、Dmitry S. Yufit

  DOI：10.1016/j.tetlet.2012.08.063

  日期：2012.10

  dimethyl diazomalonate with methyl 2-bromo- and 2-chloro-3-phenyl-2H-azirine-2-carboxylates gives rise to electron-poor 4-halo-substituted (3E)-2-azabuta-1,3-dienes. Their formation proceeds with complete stereoselectivity via ring-opening of the intermediate azirinium ylide. 2-Azabuta-1,3-dienes with electron-withdrawing substituents at the 1,1,4-positions are stable compounds at room temperature, but

  Rh 2（OAc）4催化2-酰基-2-重氮乙酸烷基酯和重氮丙二酸二甲酯与2-溴-和2-氯-3-苯基-2 H-叠氮基-2-羧酸甲酯的反应弱的4-卤代（3 E）-2-azabuta-1,3-二烯。它们的形成通过中间的叠氮基内鎓盐的开环以完全的立体选择性进行。在1,1,4-位置带有吸电子取代基的2-氮杂丁1,3-二烯在室温下是稳定的化合物，但在高温下与环状价异构体2,3-二氢氮杂环丁烷处于平衡状态。
• Acid-catalyzed rearrangement of 1-acyl-2-azabuta-1,3-dienes to 4-pyrrolin-2-ones
  作者：Nikolai V. Rostovskii、Ilia A. Smetanin、Alexander N. Koronatov、Anastasiya V. Agafonova、Vasilii V. Potapenkov、Alexander F. Khlebnikov、Mikhail S. Novikov

  DOI：10.1007/s10593-020-02745-x

  日期：2020.7

  1-acetyl-2-azabuta-1,3-dienes were stable toward rearrangement, while brominated analogs rearranged into 4-pyrrolin-2-ones, probably as a result of the initial radical hydrodebromination. According to calculations performed at the DFT level, two steps of the reaction were catalyzed by acid: the cyclization of 2-azabutadiene and the sigmatropic shift in the 2-hydroxy-2Н-pyrrole intermediate.

  在酸性催化剂（硅胶或ZnCl 2）和水的存在下，将1-酰基-2-azabuta-1，3-二烯进行重排，生成4-吡咯啉-2-酮。该反应通过形成2,3-二羟基-3,4-二氢吡咯和2-羟基-2Н-吡咯中间体而进行，中间体通过羰基取代基的[1,5]-σ位移和质子异构化而转化。4-氯取代的1-乙酰基-2-azabuta-1,3-二烯对重排稳定，而溴化类似物重排成4-吡咯啉-2-酮，这可能是由于最初的自由基加氢脱溴作用所致。根据在DFT级进行的计算，酸催化了反应的两个步骤：2-氮杂丁二烯的​​环化和2-羟基-2的σ位移Н-吡咯中间体。