methyl (2E)-2-bromo-3-(1-methoxy-1,3-dioxo-3-phenylpropan-2-ylideneamino)-3-phenylacrylate | 1403871-53-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl (2E)-2-bromo-3-(1-methoxy-1,3-dioxo-3-phenylpropan-2-ylideneamino)-3-phenylacrylate
• 英文别名: methyl (E)-2-bromo-3-[(1-methoxy-1,3-dioxo-3-phenylpropan-2-ylidene)amino]-3-phenylprop-2-enoate
• CAS: 1403871-53-3
• 化学式: C₂₀H₁₆BrNO₅
• 分子量: 430.255
• InChiKey: UMUAENAPMVNOQD-SJWGCNSXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.1
• 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：

  methyl (2E)-2-bromo-3-(1-methoxy-1,3-dioxo-3-phenylpropan-2-ylideneamino)-3-phenylacrylate 在 potassium carbonate 作用下， 以 苯 为溶剂， 反应 1.0h， 以25%的产率得到dimethyl 2-benzoyl-3-bromo-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：

  2-diazo-3-oxo-3-phenyl-propionic acid methyl ester 、 methyl 2-bromo-3-phenyl-2H-azirine-2-carboxylate 在 dirhodium tetraacetate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.01h， 以83%的产率得到methyl (2E)-2-bromo-3-(1-methoxy-1,3-dioxo-3-phenylpropan-2-ylideneamino)-3-phenylacrylate
  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。