2-(3-methoxy-1-propynyl)-α-diazoacetophenone | 133446-19-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(3-methoxy-1-propynyl)-α-diazoacetophenone
• 英文别名: 2-Diazo-1-[2-(3-methoxyprop-1-ynyl)phenyl]ethanone；2-diazo-1-[2-(3-methoxyprop-1-ynyl)phenyl]ethanone
• CAS: 133446-19-2
• 化学式: C₁₂H₁₀N₂O₂
• 分子量: 214.224
• InChiKey: KKBQDOFNNQLZMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  28.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(3-methoxy-1-propynyl)-α-diazoacetophenone 生成 3-((E)-2-methoxyethen-1-yl)-1-oxo-1H-indene
  参考文献：
  名称：

  PADWA, ALBERT;KRUMPE, KEITH E.;GAREAU, YVES;CHIACCHIO, UGO, J. ORG. CHEM., 56,(1991) N, C. 2523-2530

  摘要：

  DOI：
• 作为产物：
  描述：

  2-碘苯甲酸甲酯 在 copper(l) iodide 、 bis(triphenylphosphine)palladium(II)-chloride 、 三苯基膦 potassium trimethylsilonate 、 三乙胺 、 氯甲酸甲酯 作用下， 反应 16.0h， 生成 2-(3-methoxy-1-propynyl)-α-diazoacetophenone
  参考文献：
  名称：

  Rhodium(II)-catalyzed cyclization reactions of alkynyl-substituted .alpha.-diazo ketones

  摘要：

  Treatment of several omicron-alkynl-substituted alpha-diazoacetophenone derivatives with rhodium (II) carboxylates results in the formation of substituted indenones. The simplest mechanism accounting for the results involves addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to generate a vinyl carbenoid directly of possibly a highly strained cyclopropene derivative. The vinyl carbenoid was found to undergo addition to a neighboring alkene tethered on the side chain to give an indenyl-substituted bicyclo[3.1.0]hexane derivative. A number of related systems were examined so as to probe the scope and generality of the process. Treatment of omicron-(6,8-nonadien-1-ynyl)-alpha-diazoacetophenone with rhodium (II) mandelate afforded a cyclopent[g]azulenone derivative. The formation of this compound involves a divinylcyclopropane intermediate that readily undergoes a Cope rearrangement under the reaction conditions. The rhodium-catalyzed reaction of 2-(6-oxo-1-hepty-nyl)-alpha-diazoacetophenone in the presence of N-phenylmaleimide afforded a mixture of two cycloadducts. One of the products can be accounted for in terms of a cyclization of the vinyl carbenoid onto the oxygen atom of the neighboring carbonyl group to give a resonance-stabilized dipole. 1,3-Dipolar cycloaddition of the carbonyl ylide across the activated pi-bond of N-phenylmaleimide affords the observed product. The second cycloadduct is formed by a 1,2-hydrogen shift of the initially produced vinyl carbenoid. The resulting diene undergoes a subsequent Diels-Alder reactions with N-phenylmaleimide.

  DOI：

  10.1021/jo00007a047

文献信息

• Rhodium(II)-catalyzed cyclization reactions of alkynyl-substituted .alpha.-diazo ketones
  作者：Albert Padwa、Keith E. Krumpe、Yves Gareau、Ugo Chiacchio

  DOI：10.1021/jo00007a047

  日期：1991.3

  Treatment of several omicron-alkynl-substituted alpha-diazoacetophenone derivatives with rhodium (II) carboxylates results in the formation of substituted indenones. The simplest mechanism accounting for the results involves addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to generate a vinyl carbenoid directly of possibly a highly strained cyclopropene derivative. The vinyl carbenoid was found to undergo addition to a neighboring alkene tethered on the side chain to give an indenyl-substituted bicyclo[3.1.0]hexane derivative. A number of related systems were examined so as to probe the scope and generality of the process. Treatment of omicron-(6,8-nonadien-1-ynyl)-alpha-diazoacetophenone with rhodium (II) mandelate afforded a cyclopent[g]azulenone derivative. The formation of this compound involves a divinylcyclopropane intermediate that readily undergoes a Cope rearrangement under the reaction conditions. The rhodium-catalyzed reaction of 2-(6-oxo-1-hepty-nyl)-alpha-diazoacetophenone in the presence of N-phenylmaleimide afforded a mixture of two cycloadducts. One of the products can be accounted for in terms of a cyclization of the vinyl carbenoid onto the oxygen atom of the neighboring carbonyl group to give a resonance-stabilized dipole. 1,3-Dipolar cycloaddition of the carbonyl ylide across the activated pi-bond of N-phenylmaleimide affords the observed product. The second cycloadduct is formed by a 1,2-hydrogen shift of the initially produced vinyl carbenoid. The resulting diene undergoes a subsequent Diels-Alder reactions with N-phenylmaleimide.
• PADWA, ALBERT;KRUMPE, KEITH E.;GAREAU, YVES;CHIACCHIO, UGO, J. ORG. CHEM., 56,(1991) N, C. 2523-2530
  作者：PADWA, ALBERT、KRUMPE, KEITH E.、GAREAU, YVES、CHIACCHIO, UGO

  DOI：——

  日期：——