1-<2-Oxo-3-(but-3-enyl)pyrrolidinyl>-2-diazobutane-1,3-dione | 144396-81-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1-<2-Oxo-3-(but-3-enyl)pyrrolidinyl>-2-diazobutane-1,3-dione
• 英文别名: 4-[3-(But-3-en-1-yl)-2-oxopyrrolidin-1-yl]-3-diazonio-4-oxobut-2-en-2-olate；1-(3-but-3-enyl-2-oxopyrrolidin-1-yl)-2-diazobutane-1,3-dione
• CAS: 144396-81-6
• 化学式: C₁₂H₁₅N₃O₃
• 分子量: 249.269
• InChiKey: LGLJJCKBASDTGL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  88.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-<2-Oxo-3-(but-3-enyl)pyrrolidinyl>-2-diazobutane-1,3-dione 在 rhodium(II) acetate dimer 作用下， 以 苯 为溶剂， 以88%的产率得到5-Acetyl-1,2,4,5,6,6a,7,8,8a,8b-decahydro-5,8b-epoxy-4-oxocyclopentindolizine
  参考文献：
  名称：

  铑（II）催化的重氮酰亚胺环化反应生成异麦草酮的分子内环加成反应

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(00)61271-6
• 作为产物：
  描述：

  3-(丁-3-烯-1-基)吡咯烷-2-酮 在 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 乙腈 、 xylene 为溶剂， 反应 5.0h， 生成 1-<2-Oxo-3-(but-3-enyl)pyrrolidinyl>-2-diazobutane-1,3-dione
  参考文献：
  名称：

  Studies on the Intramolecular Cycloaddition Reaction of Mesoionics Derived from the Rhodium(II)-Catalyzed Cyclization of Diazoimides

  摘要：

  A series of alkenyl-substituted imides were prepared by treating the appropriate amide with 2,2,6-trimethyl-4H-1,3-dioxen-4-one in xylene at 140-degrees-C to give the N-acetoacylated imides. Exposure of these imides to standard diazo transfer conditions gave the desired diazoimides. The carbenoid intermediate derived by treatment of the diazoimide with rhodium(II) acetate undergoes ready cyclization onto the neighboring amide carbonyl oxygen atom to generate an isomunchnone intermediate. Subsequent 1,3-dipolar cycloaddition across the pendant olefin affords the cycloadduct in high yield. The stereochemical assignment of several of the cycloadducts was deduced by X-ray crystallography. The stereochemical outcome of the reaction is the consequence of an endo cycloaddition of the neighboring pi-bond across the transient isomunchnone dipole. Molecular mechanics calculations were used to model energy differences between the endo and exo diastereomers. The calculations reveal that the endo diastereomers are significantly (8-12 kcal/mol) lower in energy than the corresponding exo isomers thereby providing a rationale for the preferred endo cycloaddition. Ring opening of the cycloadducts occurred readily producing a transient N-acyliminium ion which either lost a proton to give an enamide or was reduced by Et3SiH to afford a bicyclic piperidine ring.

  DOI：

  10.1021/jo00085a035

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。
• Studies on the Intramolecular Cycloaddition Reaction of Mesoionics Derived from the Rhodium(II)-Catalyzed Cyclization of Diazoimides
  作者：Albert Padwa、Donald L. Hertzog、William R. Nadler、Martin H. Osterhout、Alan T. Price

  DOI：10.1021/jo00085a035

  日期：1994.3

  A series of alkenyl-substituted imides were prepared by treating the appropriate amide with 2,2,6-trimethyl-4H-1,3-dioxen-4-one in xylene at 140-degrees-C to give the N-acetoacylated imides. Exposure of these imides to standard diazo transfer conditions gave the desired diazoimides. The carbenoid intermediate derived by treatment of the diazoimide with rhodium(II) acetate undergoes ready cyclization onto the neighboring amide carbonyl oxygen atom to generate an isomunchnone intermediate. Subsequent 1,3-dipolar cycloaddition across the pendant olefin affords the cycloadduct in high yield. The stereochemical assignment of several of the cycloadducts was deduced by X-ray crystallography. The stereochemical outcome of the reaction is the consequence of an endo cycloaddition of the neighboring pi-bond across the transient isomunchnone dipole. Molecular mechanics calculations were used to model energy differences between the endo and exo diastereomers. The calculations reveal that the endo diastereomers are significantly (8-12 kcal/mol) lower in energy than the corresponding exo isomers thereby providing a rationale for the preferred endo cycloaddition. Ring opening of the cycloadducts occurred readily producing a transient N-acyliminium ion which either lost a proton to give an enamide or was reduced by Et3SiH to afford a bicyclic piperidine ring.