ethyl 3-(1-acetylcyclopropyl)-2-diazo-3-oxopropionate | 155853-83-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3-(1-acetylcyclopropyl)-2-diazo-3-oxopropionate
• 英文别名: Ethyl 3-(1-acetylcyclopropyl)-2-diazo-3-oxopropanoate
• CAS: 155853-83-1
• 化学式: C₁₀H₁₂N₂O₄
• 分子量: 224.216
• InChiKey: NEXVVXLMLFSJQZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  62.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 3-(1-acetylcyclopropyl)-2-diazo-3-oxopropionate 在 甲醇 、 samarium diiodide 、 rhodium⁽²⁺⁾ 作用下， 以 四氢呋喃 为溶剂， 生成 ethyl 2,2-dimethoxy-5-ethyl-4-methyl-6-oxo-7-oxabicyclo<2.2.1>heptane-1-carboxylate
  参考文献：
  名称：

  Synthetic studies toward Illudins and Ptaquilosin. A highly convergent approach via the dipolar cycloaddition of carbonyl ylides

  摘要：

  DOI：

  10.1021/ja00085a076
• 作为产物：
  描述：

  1-乙酰基-环丙烷羧酸 在 异丙基溴化镁 、 三乙胺 、 甲烷磺酰基叠氮化物 、 N,N'-羰基二咪唑 作用下， 反应 8.5h， 生成 ethyl 3-(1-acetylcyclopropyl)-2-diazo-3-oxopropionate
  参考文献：
  名称：

  Generation and Cycloaddition Behavior of Spirocyclic Carbonyl Ylides. Application to the Synthesis of the Pterosin Family of Sesquiterpenes

  摘要：

  The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)cyclopropane and ethyl 3-(1-acetyl-cyclopropyl)-2-diazo-3-oxopropiolate with various dipolarophiles afforded dipolar cycloadducts in good yield. The reaction involves the formation of a rhodium carbenoid and subsequent transannular cyclization of the electrophilic carbon onto the adjacent keto group to generate a five-membered cyclic carbonyl ylide which undergoes a subsequent dipolar cycloaddition reaction. The regiochemical results encountered can be rationalized on the basis of FMO considerations. For carbonyl ylides, the HOMO dipole is dominant for reactions with electron deficient dipolarophiles, while the LUMO becomes important for cycloaddition to more electron rich species. A short synthesis of several members of the pterosin family of sesquiterpenes is described in which the key step involves a dipolar cycloaddition using a carbonyl ylide. The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)-cyclopropane with cyclopentenone afforded a dipolar cycloadduct in good yield as a 4:1 mixture of diastereomers. Treatment of the major cycloadduct with triphenylphosphonium bromide in the presence of sodium hydride gave the expected Wittig product. The reaction of this compound with acid in the presence of various solvents gave rise to several members of the pterosin family. The overall sequence of reactions can best be described as proceeding by an initial oxy-bridge ring opening followed by dehydration and a subsequent acid-catalyzed cyclopropyl ring opening. The facility of the process is undoubtedly related to the aromaticity gained in the final step.

  DOI：

  10.1021/jo951371e

文献信息

• Cyclization of rhodium carbenoids using ester and amido carbonyl groups
  作者：Erin A. Curtis、Kimberly J. Worsencroft、Albert Padwa

  DOI：10.1016/s0040-4039(97)00617-5

  日期：1997.5

  Carbonyl ylide dipoles derived from diazoacetyl esters underwent 4 pi-electrocyclization to furnish bicyclic epoxides. Reaction of related alpha-diazoketo amides with rhodium(II) carboxylate catalysts resulted in cyclization on both the oxygen and nitrogen atoms of the amido group to give carbonyl and ammonium ylides. (C) 1997 Elsevier Science Ltd.