2-propynyl 2-diazo-3-oxoheptanoate | 144713-01-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-propynyl 2-diazo-3-oxoheptanoate
• 英文别名: Prop-2-ynyl 2-diazo-3-oxoheptanoate
• CAS: 144713-01-9
• 化学式: C₁₀H₁₂N₂O₃
• 分子量: 208.217
• InChiKey: NEUAZASNFXFPBQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  45.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-propynyl 2-diazo-3-oxoheptanoate 在 rhodium(II) acetate dimer 作用下， 以 苯 为溶剂， 生成 1-oxo-6-butyl-1H,3H-furo<3,4-c>furan 、 2-propynyl 2-oxo-5-methylcyclopentane-1-carboxylate
  参考文献：
  名称：

  Rhodium(II)-catalyzed cyclization of 2-alkynyl 2-diazo-3-oxobutanoates as a method for synthesizing substituted furans

  摘要：

  A series of 2-alkynyl 2-diazo-3-oxobutanoates, when treated with a catalytic quantity of rhodium(II) acetate, were found to produce furo[3,4-c]furans in good yield. The reaction proceeds by addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. In a similar manner, indeno[1,2-c]furans were produced from 2-butynyl 2-diazoarylacetates. Compounds substituted with methyl groups on the propargylic carbon atom cyclized at a slower rate. This rate diminution is attributed to the fact that the unsubstituted propargyl group can more easily achieve the required conformation for cyclization. C-H insertion was found to compete with furan formation when an alkyl group was attached to the keto functionality of the starting diazo acetoacetate. Diazo alkynyl sulfones undergo a novel oxygen transfer reaction when treated with rhodium(II) acetate at 80-degrees-C. The cyclized product is formed by sulfone oxygen attack onto the vinyl carbenoid producing a dipolar species which subsequently collapses to give the butenolide sulfoxide.

  DOI：

  10.1021/jo00053a009
• 作为产物：
  描述：

  2-propynyl 2-diazo-3-oxobutanoate 在 四氢吡咯 、 三乙胺 、 甲烷磺酰基叠氮化物 、 tin(ll) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 2-propynyl 2-diazo-3-oxoheptanoate
  参考文献：
  名称：

  Rhodium(II)-catalyzed cyclization of 2-alkynyl 2-diazo-3-oxobutanoates as a method for synthesizing substituted furans

  摘要：

  A series of 2-alkynyl 2-diazo-3-oxobutanoates, when treated with a catalytic quantity of rhodium(II) acetate, were found to produce furo[3,4-c]furans in good yield. The reaction proceeds by addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. In a similar manner, indeno[1,2-c]furans were produced from 2-butynyl 2-diazoarylacetates. Compounds substituted with methyl groups on the propargylic carbon atom cyclized at a slower rate. This rate diminution is attributed to the fact that the unsubstituted propargyl group can more easily achieve the required conformation for cyclization. C-H insertion was found to compete with furan formation when an alkyl group was attached to the keto functionality of the starting diazo acetoacetate. Diazo alkynyl sulfones undergo a novel oxygen transfer reaction when treated with rhodium(II) acetate at 80-degrees-C. The cyclized product is formed by sulfone oxygen attack onto the vinyl carbenoid producing a dipolar species which subsequently collapses to give the butenolide sulfoxide.

  DOI：

  10.1021/jo00053a009