5-((E)-2-Methoxycarbonyl-vinyl)-2-methyl-furan-3-carboxylic acid ethyl ester | 144463-27-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃
• 英文名称: 5-((E)-2-Methoxycarbonyl-vinyl)-2-methyl-furan-3-carboxylic acid ethyl ester
• 英文别名: ethyl 5-[(E)-3-methoxy-3-oxoprop-1-enyl]-2-methylfuran-3-carboxylate
• CAS: 144463-27-4
• 化学式: C₁₂H₁₄O₅
• 分子量: 238.24
• InChiKey: ANQHQTXFAKNOAW-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.95
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  65.74
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  5-((E)-2-Methoxycarbonyl-vinyl)-2-methyl-furan-3-carboxylic acid ethyl ester 在 氢氧化钾 作用下， 以 水 为溶剂， 反应 1.0h， 以66%的产率得到(E)-3-(4-carboxy-5-methyl-2-furyl)propenoic acid
  参考文献：
  名称：

  Synthesis of 3-(5-Alkyl-4-acetyl(ethoxycarbonyl))-2-propenoates from Derivatives of 3-Phenoxy-2-furylmethylene

  摘要：

  通过用酒精性氢氯酸一步处理5-苯氧基-2-呋喃甲醛衍生物I-III，得到了3-(2-呋喃基)丙烯酸酯IV-VIII。文中还介绍了可能的合成路线，将合成原料I-III转化为2,4,5-三取代呋喃。分离出的几何异构体E-IV、Z-V和Z-VI被碱催化水解转化为相应的酸E-IX、Z-IX和E-X。将1,3-二酮I酸水解后得到(4Z,6Z)-6-乙酰基-7-羟基-2,4,6-辛三烯-4-酮（XI）。通过光谱（红外、紫外、核磁共振和质谱）方法验证了产物的结构。

  DOI：

  10.1135/cccc19921684
• 作为产物：
  描述：

  、 乙酰乙酸乙酯 在 indium(III) triflate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 6.0h， 以68%的产率得到5-((E)-2-Methoxycarbonyl-vinyl)-2-methyl-furan-3-carboxylic acid ethyl ester
  参考文献：
  名称：

  Piano-Stool Rhodium Enalcarbenoids: Application to Catalyst-Controlled Metal-Templated Annulations of Diazoenals and 1,3-Dicarbonyls

  摘要：

  An electrophilic piano-stool rhodium(III)-enalcarbenoid resulted from the reaction of diazoenal with the cationic Cp*Rh-III in the presence of a 1,3-diketone. The synthetic utility of these transient carbenoids has been demonstrated in the metal-templated [3 + 2] annulation of diazoenals and 1,3-dicarbonyls, thus leading to the enal-functionalized tetrasubstituted furans. The significance of the piano-stool enalcarbenoids has been further exemplified by the mechanistically distinct, complementary Lewis acid templated [2 + 3] annulation of diazoenals and 1,3-dicarbonyls, resulting in the trisubstituted furanyl-enones and acrylates. Mechanistic investigations revealed that these annulations proceed through catalyst-dependent chemoselective activation of diazoenal by the in situ formed metal diketonates. These methodologies gave access to core structures of indeno[1,2-b]furans, tetracyclic OLED, and a pan-AKT inhibitor.

  DOI：

  10.1021/acscatal.8b03865

文献信息

• Piano-Stool Rhodium Enalcarbenoids: Application to Catalyst-Controlled Metal-Templated Annulations of Diazoenals and 1,3-Dicarbonyls
  作者：Bapurao Sudam Lad、Sreenivas Katukojvala

  DOI：10.1021/acscatal.8b03865

  日期：2018.12.7

  An electrophilic piano-stool rhodium(III)-enalcarbenoid resulted from the reaction of diazoenal with the cationic Cp*Rh-III in the presence of a 1,3-diketone. The synthetic utility of these transient carbenoids has been demonstrated in the metal-templated [3 + 2] annulation of diazoenals and 1,3-dicarbonyls, thus leading to the enal-functionalized tetrasubstituted furans. The significance of the piano-stool enalcarbenoids has been further exemplified by the mechanistically distinct, complementary Lewis acid templated [2 + 3] annulation of diazoenals and 1,3-dicarbonyls, resulting in the trisubstituted furanyl-enones and acrylates. Mechanistic investigations revealed that these annulations proceed through catalyst-dependent chemoselective activation of diazoenal by the in situ formed metal diketonates. These methodologies gave access to core structures of indeno[1,2-b]furans, tetracyclic OLED, and a pan-AKT inhibitor.
• Synthesis of 3-(5-Alkyl-4-acetyl(ethoxycarbonyl))-2-propenoates from Derivatives of 3-Phenoxy-2-furylmethylene
  作者：Štefan Marchalín、Vladimír Mlynárik、Anna Staňová、Dušan Ilavský

  DOI：10.1135/cccc19921684

  日期：——

  3-(2-Furyl)propenoates IV-VIII were obtained by treatment of 5-phenoxy-2-furylmethylene derivatives I-III with alcoholic hydrogen chloride in one step. The probable transition mechanism of synthons I-III into the 2,4,5-trisubstituted furans is presented. The geometric isomers E-IV, Z-V and Z-VI, isolated in pure form, were transformed into the corresponding acids E-IX, Z-IX and E-X by base-catalyzed hydrolysis. Acid hydrolysis of the 1,3-diketone I afforded (4Z,6Z)-6-acetyl-7-hydroxy-2,4,6-octatrien-4-olide (XI). Structure of the products was verified by spectral (IR, UV, NMR and mass) methods.

  通过用酒精性氢氯酸一步处理5-苯氧基-2-呋喃甲醛衍生物I-III，得到了3-(2-呋喃基)丙烯酸酯IV-VIII。文中还介绍了可能的合成路线，将合成原料I-III转化为2,4,5-三取代呋喃。分离出的几何异构体E-IV、Z-V和Z-VI被碱催化水解转化为相应的酸E-IX、Z-IX和E-X。将1,3-二酮I酸水解后得到(4Z,6Z)-6-乙酰基-7-羟基-2,4,6-辛三烯-4-酮（XI）。通过光谱（红外、紫外、核磁共振和质谱）方法验证了产物的结构。