α-methoxycarbonyl-α-ethyl-γ-methylidene-δ-valerolactone | 1198581-73-5

• 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: α-methoxycarbonyl-α-ethyl-γ-methylidene-δ-valerolactone
• 英文别名: Methyl 3-ethyl-5-methylidene-2-oxooxane-3-carboxylate；methyl 3-ethyl-5-methylidene-2-oxooxane-3-carboxylate
• CAS: 1198581-73-5
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: BUBDNFNASMGIJZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  α-methoxycarbonyl-α-ethyl-γ-methylidene-δ-valerolactone 、 环丙烷-1,1-二腈 在 allyl(cyclopentadiene)palladium(II) 、 N,N-diethylbenzo[d][1,3,2]benzodioxaphosphepin-6-amine 作用下， 以 甲苯 为溶剂， 反应 48.08h， 以72%的产率得到methyl 7,7-dicyano-3-ethyl-5-methylene-2-oxooxonane-3-carboxylate
  参考文献：
  名称：

  Palladium-Catalyzed Decarboxylative [4 + 3] Cyclization of γ-Methylidene-δ-valerolactones with 1,1-Dicyanocyclopropanes

  摘要：

  A palladium-catalyzed decarboxylative [4 + 3] cyclization of gamma-methylidene-delta-valerolactones with 1,1-dicyanocyclopropanes has been developed to produce cycloheptane derivatives in a convergent manner. This method can be applied to the synthesis of azepanes by reacting with aziridines, and their asymmetric variants have also been described. In addition, selective ring-expansion reactions can be achieved for certain gamma-methylidene-delta-valerolactones to give nondecarboxylated nine-membered lactones.

  DOI：

  10.1021/ol902326s
• 作为产物：
  描述：

  乙基丙二酸二甲酯 、 2-(tert-butyldimethylsiloxy)methyl-2-propen-1-yl methanesulfonate 在 sodium hydride 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 27.4h， 以50%的产率得到α-methoxycarbonyl-α-ethyl-γ-methylidene-δ-valerolactone
  参考文献：
  名称：

  Palladium-Catalyzed Decarboxylative [4 + 3] Cyclization of γ-Methylidene-δ-valerolactones with 1,1-Dicyanocyclopropanes

  摘要：

  A palladium-catalyzed decarboxylative [4 + 3] cyclization of gamma-methylidene-delta-valerolactones with 1,1-dicyanocyclopropanes has been developed to produce cycloheptane derivatives in a convergent manner. This method can be applied to the synthesis of azepanes by reacting with aziridines, and their asymmetric variants have also been described. In addition, selective ring-expansion reactions can be achieved for certain gamma-methylidene-delta-valerolactones to give nondecarboxylated nine-membered lactones.

  DOI：

  10.1021/ol902326s

文献信息

• Palladium-Catalyzed Decarboxylative [4 + 3] Cyclization of γ-Methylidene-δ-valerolactones with 1,1-Dicyanocyclopropanes
  作者：Ryo Shintani、Masataka Murakami、Takaoki Tsuji、Hideyuki Tanno、Tamio Hayashi

  DOI：10.1021/ol902326s

  日期：2009.12.17

  A palladium-catalyzed decarboxylative [4 + 3] cyclization of gamma-methylidene-delta-valerolactones with 1,1-dicyanocyclopropanes has been developed to produce cycloheptane derivatives in a convergent manner. This method can be applied to the synthesis of azepanes by reacting with aziridines, and their asymmetric variants have also been described. In addition, selective ring-expansion reactions can be achieved for certain gamma-methylidene-delta-valerolactones to give nondecarboxylated nine-membered lactones.