[(2S,3R)-3-Acetyl-1-(2,2-dimethyl-propyl)-4-oxo-azetidin-2-yl]-acetic acid ethyl ester | 126556-97-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: [(2S,3R)-3-Acetyl-1-(2,2-dimethyl-propyl)-4-oxo-azetidin-2-yl]-acetic acid ethyl ester
• 英文别名: ethyl 2-[(2S,3R)-3-acetyl-1-(2,2-dimethylpropyl)-4-oxoazetidin-2-yl]acetate
• CAS: 126556-97-6
• 化学式: C₁₄H₂₃NO₄
• 分子量: 269.341
• InChiKey: SQLXYRDHODUEKV-JQWIXIFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  63.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  ethyl 3-(N-neopentyl-N-(diazoacetoacetyl)amino)propanoate 在 dirhodium(II) tetrakis(perfluorobutyrate) 作用下， 以 苯 为溶剂， 反应 3.0h， 生成 2-Acetyl-4-(2,2-dimethyl-propyl)-7-ethoxy-4,5-dihydro-[1,4]oxazepin-3-one 、 [(2S,3R)-3-Acetyl-1-(2,2-dimethyl-propyl)-4-oxo-azetidin-2-yl]-acetic acid ethyl ester 、 (3S,4R)-4-Acetyl-1-(2,2-dimethyl-propyl)-5-oxo-pyrrolidine-3-carboxylic acid ethyl ester
  参考文献：
  名称：

  Synthesis of nitrogen-containing polycycles via rhodium(II)-induced cyclization-cycloaddition and insertion reactions of N-(diazoacetoacetyl)amides. Conformational control of reaction selectivity

  摘要：

  A series of diazoacetoacetamides, when treated with a catalytic quantity of a rhodium(II) carboxylate, were found to afford products derived from both a carbonyl ylide intermediate and intramolecular C-H insertion. With 3-(N-(diazoacetoacetyl)amino)propanoate derivatives, the rhodium(II)-catalyzed carbenoid reactions exhibit a strong preference for formation of a beta-lactam ring. This is attributed to a conformational preference that juxtaposes the carbenoid center and the less sterically encumbered amide substituent and is consistent with an activating influence on the C-H bond adjacent to the amide nitrogen atom. Carbonyl ylide products derived from carbenoid cyclization onto the ester carbonyl group are also formed, and their relative yields are dependent on electronic influences from the bridging ligands of rhodium(II). Treatment of a series of cyclic diazoimides with rhodium(II) acetate resulted in cyclization of the rhodium carbenoid onto the adjacent imide carbonyl group to produce an isomunchnone dipole. Cyclization onto the imide carbonyl group occurs exclusively even when C-H insertion or aromatic substitution reactions of the carbenoid intermediate are favorable, and this selectivity is also attributed to conformational preferences that juxtapose the carbenoid center and imide carbonyl group. The isomunchnone dipole readily undergoes cycloaddition with several different dipolarophiles to give 1,3-dipolar cycloadducts. When acetylenic dipolarophiles were used as the trapping agents, the initial cycloadducts were found to undergo a [4 + 2]-cycloreversion, producing substituted furans in high yield. The generality of the method was demonstrated by varying the ring size of the cyclic imide. An analogous cyclization-cycloaddition reaction also occurred using diazoacetoacetyl-substituted ureas.

  DOI：

  10.1021/jo00002a058

文献信息

• Synthesis of nitrogen-containing polycycles via rhodium(II)-induced cyclization-cycloaddition and insertion reactions of N-(diazoacetoacetyl)amides. Conformational control of reaction selectivity
  作者：Michael P. Doyle、Roland J. Pieters、Jack Taunton、Hoan Q. Pho、Albert Padwa、Donald L. Hertzog、Laura Precedo

  DOI：10.1021/jo00002a058

  日期：1991.1

  A series of diazoacetoacetamides, when treated with a catalytic quantity of a rhodium(II) carboxylate, were found to afford products derived from both a carbonyl ylide intermediate and intramolecular C-H insertion. With 3-(N-(diazoacetoacetyl)amino)propanoate derivatives, the rhodium(II)-catalyzed carbenoid reactions exhibit a strong preference for formation of a beta-lactam ring. This is attributed to a conformational preference that juxtaposes the carbenoid center and the less sterically encumbered amide substituent and is consistent with an activating influence on the C-H bond adjacent to the amide nitrogen atom. Carbonyl ylide products derived from carbenoid cyclization onto the ester carbonyl group are also formed, and their relative yields are dependent on electronic influences from the bridging ligands of rhodium(II). Treatment of a series of cyclic diazoimides with rhodium(II) acetate resulted in cyclization of the rhodium carbenoid onto the adjacent imide carbonyl group to produce an isomunchnone dipole. Cyclization onto the imide carbonyl group occurs exclusively even when C-H insertion or aromatic substitution reactions of the carbenoid intermediate are favorable, and this selectivity is also attributed to conformational preferences that juxtapose the carbenoid center and imide carbonyl group. The isomunchnone dipole readily undergoes cycloaddition with several different dipolarophiles to give 1,3-dipolar cycloadducts. When acetylenic dipolarophiles were used as the trapping agents, the initial cycloadducts were found to undergo a [4 + 2]-cycloreversion, producing substituted furans in high yield. The generality of the method was demonstrated by varying the ring size of the cyclic imide. An analogous cyclization-cycloaddition reaction also occurred using diazoacetoacetyl-substituted ureas.