5-(N-(carbethoxymethyl)-N-methylamino)-6,7-dicarbomethoxy-8,9-dihydro-9-oxa-5,8-epoxy-5H-benzocycloheptene | 125735-85-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 5-(N-(carbethoxymethyl)-N-methylamino)-6,7-dicarbomethoxy-8,9-dihydro-9-oxa-5,8-epoxy-5H-benzocycloheptene
• 英文别名: Dimethyl 1-[(2-ethoxy-2-oxoethyl)-methylamino]-8-oxo-12-oxatricyclo[7.2.1.02,7]dodeca-2,4,6,10-tetraene-10,11-dicarboxylate
• CAS: 125735-85-5
• 化学式: C₂₀H₂₁NO₈
• 分子量: 403.389
• InChiKey: IKCSTDLWTJOONH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  108
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  o-(N-(carbethoxymethyl)-N-methylcarbamyl)benzoic acid 在 rhodium(II) acetate dimer 、 三乙胺 、 氯甲酸甲酯 作用下， 以 苯 为溶剂， 反应 13.0h， 生成 5-(N-(carbethoxymethyl)-N-methylamino)-6,7-dicarbomethoxy-8,9-dihydro-9-oxa-5,8-epoxy-5H-benzocycloheptene
  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, Journal of the American Chemical Society, 1990, vol. 112, # 5, p. 2037 - 2038
  作者：Padwa, Albert、Zhi, Lin

  DOI：——

  日期：——