N-Acetoacetyl-ε-caprolactam | 14826-58-5

• 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: N-Acetoacetyl-ε-caprolactam
• 英文别名: NSC-183760；1-(2-Oxoazepan-1-yl)butane-1,3-dione
• CAS: 14826-58-5
• 化学式: C₁₀H₁₅NO₃
• 分子量: 197.234
• InChiKey: MEFTWYZNRUTABQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  54.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-Acetoacetyl-ε-caprolactam 在 4-乙酰氨基苯磺酰叠氮 、 C₄₁H₆₀N₄O₄ 、 Rh₂(Oct)₄ 、 zinc trifluoromethanesulfonate 、 三乙胺 作用下， 以 1,2-二氯乙烷 、 乙腈 为溶剂， 反应 4.0h， 生成 di-tert-butyl (2'S,3R,3'R,10a'R)-3'-acetyl-2,4'-dioxo-3',4',7',8',9',10'-hexahydro-2'H,6'H-spiro[indoline-3,1'-[3,10a]epoxypyrido[1,2-a]azepine]-1,2'-dicarboxylate
  参考文献：
  名称：

  异构体与亚甲基吲哚酮的催化不对称 [3+2] 环加成

  摘要：

  使用手性N , N '-二氧化物/Zn( II ) 络合物作为路易斯酸，通过将羰基原位分子内加成到卡宾铑上，实现了异明酮与亚甲基吲哚酮的有效对映选择性 [3+2] 环加成反应. 以高产率获得了一系列手性氧杂桥联的 3-螺哌啶，具有优异的 dr 和优异的 ee 值。

  DOI：

  10.1039/d1cc03685h
• 作为产物：
  描述：

  己内酰胺 、 2,2,6-三甲基-4H-1,3-二英-4-酮 以 间二甲苯 为溶剂， 生成 N-Acetoacetyl-ε-caprolactam
  参考文献：
  名称：

  异构体与亚甲基吲哚酮的催化不对称 [3+2] 环加成

  摘要：

  使用手性N , N '-二氧化物/Zn( II ) 络合物作为路易斯酸，通过将羰基原位分子内加成到卡宾铑上，实现了异明酮与亚甲基吲哚酮的有效对映选择性 [3+2] 环加成反应. 以高产率获得了一系列手性氧杂桥联的 3-螺哌啶，具有优异的 dr 和优异的 ee 值。

  DOI：

  10.1039/d1cc03685h

文献信息

• Sato, Masayuki; Kanuma, Norio; Kato, Tetsuzo, Chemical and pharmaceutical bulletin, 1982, vol. 30, # 4, p. 1315 - 1321
  作者：Sato, Masayuki、Kanuma, Norio、Kato, Tetsuzo

  DOI：——

  日期：——
• 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.
• Synthesis of AZA substituted polycycles via rhodium (II) carboxylate induced cyclization of diazoimides
  作者：Albert Padwa、Donald L. Hertzog、Richard L. Chinn

  DOI：10.1016/s0040-4039(00)99326-2

  日期：1989.1
• SATO, MASAYUKI;KANUMA, NORIO;KATO, TETSUZO, CHEM. AND PHARM. BULL., 1982, 30, N 4, 1315-1321
  作者：SATO, MASAYUKI、KANUMA, NORIO、KATO, TETSUZO

  DOI：——

  日期：——
• Catalytic asymmetric [3+2] cycloaddition of isomünchnones with methyleneindolinones
  作者：Kaixuan Wang、Chaoran Xu、Xinyue Hu、Yuqiao Zhou、Lili Lin、Xiaoming Feng

  DOI：10.1039/d1cc03685h

  日期：——

  An efficient enantioselective [3+2] cycloaddition of isomünchnones with methyleneindolinones that are generated by an in situ intramolecular addition of the carbonyl group to rhodium carbenes is realized with a chiral N,N′-dioxide/Zn(II) complex as a Lewis acid. A series of chiral oxa-bridged 3-spiropiperidines are obtained in high yields with excellent dr and excellent ee values.

  使用手性N , N '-二氧化物/Zn( II ) 络合物作为路易斯酸，通过将羰基原位分子内加成到卡宾铑上，实现了异明酮与亚甲基吲哚酮的有效对映选择性 [3+2] 环加成反应. 以高产率获得了一系列手性氧杂桥联的 3-螺哌啶，具有优异的 dr 和优异的 ee 值。