1,4-bis(2-diazo-3-oxobutoxy)-2-butyne

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1,4-bis(2-diazo-3-oxobutoxy)-2-butyne
• 英文别名: 4-(2-Diazo-3-oxobutanoyl)oxybut-2-ynyl 2-diazo-3-oxobutanoate；4-(2-diazo-3-oxobutanoyl)oxybut-2-ynyl 2-diazo-3-oxobutanoate
• 化学式: C₁₂H₁₀N₄O₆
• 分子量: 306.235
• InChiKey: WKDRKIJLQFGCBN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  90.7
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1,4-bis(2-diazo-3-oxobutoxy)-2-butyne 在 dirhodium tetraacetate 作用下， 以 苯 为溶剂， 以90%的产率得到3-(2-oxo-3-acetyl-2H,5H-furan-4-yl)-2-oxo-3-acetyl-2H,5H-furan
  参考文献：
  名称：

  Preparation of oxygenated heterocycles via the cyclization reaction of α-diazo substituted alkynes

  摘要：

  DOI：

  10.1016/s0040-4039(00)97184-3
• 作为产物：
  描述：

  丁炔二醇 、 diketene 在 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 生成 1,4-bis(2-diazo-3-oxobutoxy)-2-butyne
  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

文献信息

• Preparation of oxygenated heterocycles via the cyclization reaction of α-diazo substituted alkynes
  作者：Frederick R. Kinder、Albert Padwa

  DOI：10.1016/s0040-4039(00)97184-3

  日期：1990.1
• KINDER, FREDERICK R.;PADWA, ALBERT, TETRAHEDRON LETT., 31,(1990) N7, C. 6835-6838
  作者：KINDER, FREDERICK R.、PADWA, ALBERT

  DOI：——

  日期：——
• Rhodium(II)-catalyzed cyclization of 2-alkynyl 2-diazo-3-oxobutanoates as a method for synthesizing substituted furans
  作者：Albert Padwa、Frederick R. Kinder

  DOI：10.1021/jo00053a009

  日期：1993.1

  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.