1-diazo-5-(diethylamino)pentane-2,5-dione | 125735-88-8

• 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: 1-diazo-5-(diethylamino)pentane-2,5-dione
• 英文别名: 5-diazo-N,N-diethyl-4-oxopentanamide
• CAS: 125735-88-8
• 化学式: C₉H₁₅N₃O₂
• 分子量: 197.237
• InChiKey: NUXFUFFAWPAUIB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  39.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-diazo-5-(diethylamino)pentane-2,5-dione 、 丁炔二酸二甲酯 在 dirhodium tetraacetate 作用下， 生成 4,5-dicarbomethoxy-6-trans-(N,N-diethylcarbamyl)-1-oxaspiro<2.4>hept-4-ene
  参考文献：
  名称：

  Padwa, Albert; Zhi, Lin, Journal of the American Chemical Society, 1990, vol. 112, # 5, p. 2037 - 2038

  摘要：

  DOI：
• 作为产物：
  描述：

  重氮甲烷 、 3-(二乙基氨基甲酰)丙酸 在 三乙胺 、 氯甲酸甲酯 作用下， 生成 1-diazo-5-(diethylamino)pentane-2,5-dione
  参考文献：
  名称：

  A Novel Cycloaddition Reaction of α-Diazo-γ-amido Ketones Catalyzed by Rhodium(II) Acetate. Scope and Mechanistic Details of the Process

  摘要：

  alpha-Diazo ketones containing an amido group in the gamma-position have been found to undergo a novel rhodium(II)-catalyzed cycloaddition reaction. Intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group generates a carbonyl ylide dipole as a transient species. This highly stabilized dipole does not readily undergo 1,3-dipolar cycloaddition but rather transfers a proton to produce a cyclic ketene N,O-acetal. The ketene acetal is unstable to moisture and upon standing is readily hydrolyzed to a gamma-keto delta-lactone and an amine. In the absence of any significant amount of water, the ketene N,O-acetal undergoes conjugate addition with the activated st-bond of the dipolarophile to give a zwitterion intermediate. The anionic portion of the zwitterion adds to the neighboring carbonyl group. This is followed by epoxide ring formation with charge dissipation leading to an amido-substituted spiro cyclopentyl epoxide. In certain cases a hydroxy lactone was also isolated and its formation can be attributed to the competitive hydrolysis of the zwitterionic intermediate. The Rh(II)-catalyzed reaction of the diazo ketoamide derived from N-benzylpiperidone with DMAD afforded two different types of cycloadducts. In addition to the spiro cyclopentyl epoxide, a product derived from trapping of the carbonyl ylide dipole was also obtained, thereby providing additional support for the proposed mechanism.

  DOI：

  10.1021/jo952078h

文献信息

• PADWA, ALBERT;ZHI, LIN, J. AMER. CHEM. SOC., 112,(1990) N, C. 2037-2038
  作者：PADWA, ALBERT、ZHI, LIN

  DOI：——

  日期：——
• A Novel Cycloaddition Reaction of α-Diazo-γ-amido Ketones Catalyzed by Rhodium(II) Acetate. Scope and Mechanistic Details of the Process
  作者：Albert Padwa、Alan T. Price、Lin Zhi

  DOI：10.1021/jo952078h

  日期：1996.1.1

  alpha-Diazo ketones containing an amido group in the gamma-position have been found to undergo a novel rhodium(II)-catalyzed cycloaddition reaction. Intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group generates a carbonyl ylide dipole as a transient species. This highly stabilized dipole does not readily undergo 1,3-dipolar cycloaddition but rather transfers a proton to produce a cyclic ketene N,O-acetal. The ketene acetal is unstable to moisture and upon standing is readily hydrolyzed to a gamma-keto delta-lactone and an amine. In the absence of any significant amount of water, the ketene N,O-acetal undergoes conjugate addition with the activated st-bond of the dipolarophile to give a zwitterion intermediate. The anionic portion of the zwitterion adds to the neighboring carbonyl group. This is followed by epoxide ring formation with charge dissipation leading to an amido-substituted spiro cyclopentyl epoxide. In certain cases a hydroxy lactone was also isolated and its formation can be attributed to the competitive hydrolysis of the zwitterionic intermediate. The Rh(II)-catalyzed reaction of the diazo ketoamide derived from N-benzylpiperidone with DMAD afforded two different types of cycloadducts. In addition to the spiro cyclopentyl epoxide, a product derived from trapping of the carbonyl ylide dipole was also obtained, thereby providing additional support for the proposed mechanism.
• Padwa, Albert; Zhi, Lin, Journal of the American Chemical Society, 1990, vol. 112, # 5, p. 2037 - 2038
  作者：Padwa, Albert、Zhi, Lin

  DOI：——

  日期：——