4-acetoxy-4-(2-phenyl-1-methoxyethyl)-4-butanolide

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-acetoxy-4-(2-phenyl-1-methoxyethyl)-4-butanolide
• 英文别名: [2-(1-Methoxy-2-phenylethyl)-5-oxooxolan-2-yl] acetate
• 化学式: C₁₅H₁₈O₅
• 分子量: 278.305
• InChiKey: REZFIXJHZVNJEF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  2-Hydroxy-2-(1-methoxy-2-phenyl-ethyl)-cyclobutanone 、 lead tetraacetate 以 甲苯 为溶剂， 反应 1.0h， 以50%的产率得到4-acetoxy-4-(2-phenyl-1-methoxyethyl)-4-butanolide
  参考文献：
  名称：

  Radical-mediated ring enlargement of cyclobutenones: new synthetic potential of squaric acid.

  摘要：

  4-Hydroxy-2-cyclobutenones, which are readily obtainable from diethyl squarate, reacted with lead tetraacetate to give 5-acetoxy-2(5H)-furanones and 5-alkylidene-2(5H)-furanones via oxy-radical-triggered ring opening (beta-scission) and subsequent 5-endo reclosure. This method was extended to saturated four-membered alpha-ketol and applied to the synthesis of a natural product (Z-isomer of multicolanate). A carbon-centered radical-triggered reaction was also performed in which photolysis of a mixed anhydride of thiohydroxamic acid and (4-oxo-2-cyclobutenyl)acetic acid afforded a 4-cyclopentene-1,3-dione rather than the furanone as a rearranged product. The similarity of these rearrangements is discussed using a PM3 calculation in terms of pentadienoyl radical to cyclopentenone radical cyclization and its oxa version.

  DOI：

  10.1021/ja00143a006

文献信息

• Oxidative Rearrangement of 4-Hydroxy-2-cyclobutenone. A New Route to Highly Substituted Furanones from Squaric Acid
  作者：Yoshihiko Yamamoto、Masatomi Ohno、Shoji Eguchi

  DOI：10.1021/jo00096a001

  日期：1994.8

  4-Hydroxy-2-cyclobutenones, which were obtained by the reaction of diethyl squarate with an organolithium, reacted with lead tetraacetate (to generate an oxy radical) affording 5-acetoxy-2(5H)-furanones and 5-alkylidene-2(5H)-furanones. This type of rearrangement was realized in a simple four-membered cyclic alpha-ketol but not in the corresponding five-membered ring.
• Radical-mediated ring enlargement of cyclobutenones: new synthetic potential of squaric acid.
  作者：Yoshihiko Yamamoto、Masatomi Ohno、Shoji Eguchi

  DOI：10.1021/ja00143a006

  日期：1995.9

  4-Hydroxy-2-cyclobutenones, which are readily obtainable from diethyl squarate, reacted with lead tetraacetate to give 5-acetoxy-2(5H)-furanones and 5-alkylidene-2(5H)-furanones via oxy-radical-triggered ring opening (beta-scission) and subsequent 5-endo reclosure. This method was extended to saturated four-membered alpha-ketol and applied to the synthesis of a natural product (Z-isomer of multicolanate). A carbon-centered radical-triggered reaction was also performed in which photolysis of a mixed anhydride of thiohydroxamic acid and (4-oxo-2-cyclobutenyl)acetic acid afforded a 4-cyclopentene-1,3-dione rather than the furanone as a rearranged product. The similarity of these rearrangements is discussed using a PM3 calculation in terms of pentadienoyl radical to cyclopentenone radical cyclization and its oxa version.