2-Diazo-N-<4-(furan-2-yl)butyryl>-N-methyl-3-oxobutyramide | 144396-91-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-Diazo-N-<4-(furan-2-yl)butyryl>-N-methyl-3-oxobutyramide
• 英文别名: 3-diazonio-4-[4-(furan-2-yl)butanoyl-methylamino]-4-oxobut-2-en-2-olate
• CAS: 144396-91-8
• 化学式: C₁₃H₁₅N₃O₄
• 分子量: 277.28
• InChiKey: NHIWAGVWPUCTEH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.85
• 重原子数：
  20.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  103.99
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-Diazo-N-<4-(furan-2-yl)butyryl>-N-methyl-3-oxobutyramide 在 rhodium(II) acetate dimer 作用下， 以 苯 为溶剂， 反应 1.17h， 以56%的产率得到4-(Furan-2-yl)butyric acid 1-(methylcarbamoyl)-2-oxopropyl ester
  参考文献：
  名称：

  Intramolecular Cycloaddition of Isomunchnone Dipoles to Heteroaromatic .pi.-Systems

  摘要：

  A series of furanyl-, thienyl-, and indole-substituted diazo imides were prepared by treating the appropriate amides with diketene to give the N-acetoacylated imides. Exposure of the imides to standard diazo transfer conditions afforded the desired diazo imides. Treatment of these diazo imides bearing tethered heterocyclic rings with rhodium(II) acetate affords transient isomunchnone dipoles. The mesoionic dipoles are formed by cyclization of the rhodium carbenoid onto the neighboring amide carbonyl oxygen atom. The scope and limitations of the intramolecular 1,3-dipolar cycloaddition of the isomunchnones across a tethered furan and thiophene ring were studied. The facility of the internal cycloaddition is influenced by the length and nature of the tether connecting the dipole and dipolarophile functionalities. The reaction is critically dependent on conformational factors in the transition state. In addition, the first examples of intramolecular cycloaddition of isomunchnones to indole dipolarophiles are reported. Cycloadditions of this type generate highly functionalized polyheterocyclic systems with complete relative stereocontrol at the newly formed stereocenters.

  DOI：

  10.1021/jo00102a037
• 作为产物：
  描述：

  furnish 2-(3-bromopropyl)furan 在 氢氧化钾 、 正丁基锂 、 三乙胺 、 甲烷磺酰基叠氮化物 、 N,N'-羰基二咪唑 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二甲基亚砜 、 乙腈 为溶剂， 反应 46.0h， 生成 2-Diazo-N-<4-(furan-2-yl)butyryl>-N-methyl-3-oxobutyramide
  参考文献：
  名称：

  Intramolecular Cycloaddition of Isomunchnone Dipoles to Heteroaromatic .pi.-Systems

  摘要：

  A series of furanyl-, thienyl-, and indole-substituted diazo imides were prepared by treating the appropriate amides with diketene to give the N-acetoacylated imides. Exposure of the imides to standard diazo transfer conditions afforded the desired diazo imides. Treatment of these diazo imides bearing tethered heterocyclic rings with rhodium(II) acetate affords transient isomunchnone dipoles. The mesoionic dipoles are formed by cyclization of the rhodium carbenoid onto the neighboring amide carbonyl oxygen atom. The scope and limitations of the intramolecular 1,3-dipolar cycloaddition of the isomunchnones across a tethered furan and thiophene ring were studied. The facility of the internal cycloaddition is influenced by the length and nature of the tether connecting the dipole and dipolarophile functionalities. The reaction is critically dependent on conformational factors in the transition state. In addition, the first examples of intramolecular cycloaddition of isomunchnones to indole dipolarophiles are reported. Cycloadditions of this type generate highly functionalized polyheterocyclic systems with complete relative stereocontrol at the newly formed stereocenters.

  DOI：

  10.1021/jo00102a037

文献信息

• Intramolecular cycloaddition of isomünchnones derived from the rhodium(II) catalyzed cyclization of diazoimides
  作者：Donald L. Hertzog、David J. Austin、William R. Nadler、Albert Padwa

  DOI：10.1016/s0040-4039(00)61271-6

  日期：1992.8

  Rhodium(II) catalysis of various diazoimides containing tethered π-systems results in isomünchnone dipole formation followed by intramolecular dipolar-cycloaddition.

  铑（II）催化的各种含有束缚的π系统的重氮酰亚胺会导致异噻吩酮偶极形成，随后发生分子内偶极环加成反应。