ethyl 7-methylene-3-oxa-2-oxobicyclo<3.3.0>octane-1-carboxylate | 133472-45-4

• 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: ethyl 7-methylene-3-oxa-2-oxobicyclo<3.3.0>octane-1-carboxylate
• 英文别名: ethyl (3aR,6aS)-5-methylidene-3-oxo-1,4,6,6a-tetrahydrocyclopenta[c]furan-3a-carboxylate
• CAS: 133472-45-4
• 化学式: C₁₁H₁₄O₄
• 分子量: 210.23
• InChiKey: XCNDZJIWCHUAKB-LDYMZIIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  allyl-malonic acid monoethyl ester; potassium-salt 在 copper diacetate 、 四丁基溴化铵 、 sodium acetate 、 manganese triacetate 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 反应 2.0h， 生成 ethyl 7-methylene-3-oxa-2-oxobicyclo<3.3.0>octane-1-carboxylate
  参考文献：
  名称：

  Manganese(III)-mediated tandem oxidative cyclizations of .beta.-diesters. Influence of copper(II) upon the chemoselectivity of the reaction

  摘要：

  Mn(III)-mediated oxidative cyclization of esters derived from allylmalonic and benzylmalonic acids afforded through two consecutive cyclizations bislactones (17, 5) and bicyclic lactones (19, 21) or tricyclic lactones (7, 9). The ratio of these products is controlled by the stereoselectivity of the first step involving the intramolecular addition of a carbon-centered radical to a double bond. Oxidations conducted either in the presence of stoichiometric cupric ion or without added Cu(II) provide a comprehensive view of the respective influences of Mn(III) and Cu(II) upon the chemoselectivity of the reaction, which are related to their ability to oxidize radicals of different classes. For example, the primary and secondary radicals 3a and 3b, which are not efficiently oxidized by Mn(III), undergo cyclization leading to the trans fused tricyclic gamma-lactones 9a and 9b exclusively in the absence of cupric ion.

  DOI：

  10.1021/jo00009a031

文献信息

• Manganese(III)-mediated tandem oxidative cyclizations of .beta.-diesters. Influence of copper(II) upon the chemoselectivity of the reaction
  作者：M. P. Bertrand、J. M. Surzur、H. Oumar-Mahamat、C. Moustrou

  DOI：10.1021/jo00009a031

  日期：1991.4

  Mn(III)-mediated oxidative cyclization of esters derived from allylmalonic and benzylmalonic acids afforded through two consecutive cyclizations bislactones (17, 5) and bicyclic lactones (19, 21) or tricyclic lactones (7, 9). The ratio of these products is controlled by the stereoselectivity of the first step involving the intramolecular addition of a carbon-centered radical to a double bond. Oxidations conducted either in the presence of stoichiometric cupric ion or without added Cu(II) provide a comprehensive view of the respective influences of Mn(III) and Cu(II) upon the chemoselectivity of the reaction, which are related to their ability to oxidize radicals of different classes. For example, the primary and secondary radicals 3a and 3b, which are not efficiently oxidized by Mn(III), undergo cyclization leading to the trans fused tricyclic gamma-lactones 9a and 9b exclusively in the absence of cupric ion.