4-Methyl-3-pent-4-enyloxetan-2-one | 247216-22-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 4-Methyl-3-pent-4-enyloxetan-2-one
• CAS: 247216-22-4
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: LBEKYXBQAJXAPD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-Methyl-3-pent-4-enyloxetan-2-one 、 alkaline earth salt of/the/ methylsulfuric acid 以 甲苯 为溶剂， 以70%的产率得到2-Methyl-4-methylidene-3-pent-4-enyloxetane
  参考文献：
  名称：

  Preparation and Properties of 2-Methyleneoxetanes

  摘要：

  The methylenation of beta-lactones 5 with dimethyltitanocene provides a versatile, reliable, and highly chemoselective entry to 2-methyleneoxetanes 7. The conversion proceeds selectively in the presence of alkenes, unprotected alcohols, and a variety of other carbonyl moieties, A study of conditions for the optimization of this reaction is delineated. In addition, the first X-ray structure of a 2-methyleneoxetane, which shows its similarity to related p-lactones, is reported. Reactivity studies of 2-methyleneoxetanes are presented in which it is demonstrated that these compounds are attacked at C-4 with a nucleophile; then, subsequently, the resultant enolate reacted with an electrophile. An interesting dichotomy of reactivity was observed when methyleneoxetane 7c was treated with electrophiles. Reaction of 7c with acetic acid gave acetoxyoxetane 19. When 7c was exposed to bromine, dibromoketone 20 resulted.

  DOI：

  10.1021/jo9906072
• 作为产物：
  描述：

  5-碘-1-戊烯 在 氢氧化钾 、 sodium hydroxide 、 sodium tetrahydroborate 、 四丁基硫酸氢铵 、 苯磺酰氯 作用下， 以 吡啶 、 甲醇 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 25.0h， 生成 4-Methyl-3-pent-4-enyloxetan-2-one
  参考文献：
  名称：

  Preparation and Properties of 2-Methyleneoxetanes

  摘要：

  The methylenation of beta-lactones 5 with dimethyltitanocene provides a versatile, reliable, and highly chemoselective entry to 2-methyleneoxetanes 7. The conversion proceeds selectively in the presence of alkenes, unprotected alcohols, and a variety of other carbonyl moieties, A study of conditions for the optimization of this reaction is delineated. In addition, the first X-ray structure of a 2-methyleneoxetane, which shows its similarity to related p-lactones, is reported. Reactivity studies of 2-methyleneoxetanes are presented in which it is demonstrated that these compounds are attacked at C-4 with a nucleophile; then, subsequently, the resultant enolate reacted with an electrophile. An interesting dichotomy of reactivity was observed when methyleneoxetane 7c was treated with electrophiles. Reaction of 7c with acetic acid gave acetoxyoxetane 19. When 7c was exposed to bromine, dibromoketone 20 resulted.

  DOI：

  10.1021/jo9906072

文献信息

• Preparation and Properties of 2-Methyleneoxetanes
  作者：Lisa M. Dollinger、Albert J. Ndakala、Mehrnoosh Hashemzadeh、Gan Wang、Ying Wang、Isamir Martinez、Joel T. Arcari、David J. Galluzzo、Amy R. Howell、Arnold L. Rheingold、Joshua S. Figuero

  DOI：10.1021/jo9906072

  日期：1999.9.1

  The methylenation of beta-lactones 5 with dimethyltitanocene provides a versatile, reliable, and highly chemoselective entry to 2-methyleneoxetanes 7. The conversion proceeds selectively in the presence of alkenes, unprotected alcohols, and a variety of other carbonyl moieties, A study of conditions for the optimization of this reaction is delineated. In addition, the first X-ray structure of a 2-methyleneoxetane, which shows its similarity to related p-lactones, is reported. Reactivity studies of 2-methyleneoxetanes are presented in which it is demonstrated that these compounds are attacked at C-4 with a nucleophile; then, subsequently, the resultant enolate reacted with an electrophile. An interesting dichotomy of reactivity was observed when methyleneoxetane 7c was treated with electrophiles. Reaction of 7c with acetic acid gave acetoxyoxetane 19. When 7c was exposed to bromine, dibromoketone 20 resulted.