cis-3-(ethoxycarbonyl)-2,2,4-trimethyl-5-hexen-4-olide | 144734-85-0

• 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: cis-3-(ethoxycarbonyl)-2,2,4-trimethyl-5-hexen-4-olide
• 英文别名: ethyl (2S,3S)-2-ethenyl-2,4,4-trimethyl-5-oxooxolane-3-carboxylate
• CAS: 144734-85-0；144734-86-1
• 化学式: C₁₂H₁₈O₄
• 分子量: 226.273
• InChiKey: GHMBDEALKUNGAJ-UFBFGSQYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 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：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  ethyl 2,2-dimethoxy-3,3-dimethylcyclopropanecarboxylate 、 丁烯酮 在 溴化钛(IV) 、 对甲苯磺酸 作用下， 生成 trans-3-(ethoxycarbonyl)-2,2,4-trimethyl-5-hexen-4-olide 、 cis-3-(ethoxycarbonyl)-2,2,4-trimethyl-5-hexen-4-olide
  参考文献：
  名称：

  Diastereoselective ring-opening aldol-type reaction of 2,2-dialkoxycyclopropanecarboxylic esters with carbonyl compounds. 1. Synthesis of cis 3,4-substituted .gamma.-lactones

  摘要：

  The Lewis acid-promoted reactions of 2,2-dialkoxycyclopropanecarboxylic esters 4a-c with aldehydes and unsymmetrical ketones to give gamma-lactones were investigated. TiBr, is an excellent catalyst and gives cis 3,4-substituted gamma-lactones in good yields with high diastereoselectivity. SnBr4 promotes the reaction of 4a-c with aldehydes with high cis-selectivity, but does not promote the reaction of 4a with unsymmetrical ketones. ZrCl4 is moderately trans-selective in the reaction of 4a with aldehydes, while being moderately cis-selective in the reaction of 4a with unsymmetrical ketones. Cis-gamma-lactones can be converted into their trans-isomers by treatment with NaOEt in EtOH.

  DOI：

  10.1021/jo00052a028

文献信息

• Diastereoselective ring-opening aldol-type reaction of 2,2-dialkoxycyclopropanecarboxylic esters with carbonyl compounds. 1. Synthesis of cis 3,4-substituted .gamma.-lactones
  作者：Shigeru Shimada、Yukihiko Hashimoto、Atsushi Sudo、Masaki Hasegawa、Kazuhiko Saigo

  DOI：10.1021/jo00052a028

  日期：1992.12

  The Lewis acid-promoted reactions of 2,2-dialkoxycyclopropanecarboxylic esters 4a-c with aldehydes and unsymmetrical ketones to give gamma-lactones were investigated. TiBr, is an excellent catalyst and gives cis 3,4-substituted gamma-lactones in good yields with high diastereoselectivity. SnBr4 promotes the reaction of 4a-c with aldehydes with high cis-selectivity, but does not promote the reaction of 4a with unsymmetrical ketones. ZrCl4 is moderately trans-selective in the reaction of 4a with aldehydes, while being moderately cis-selective in the reaction of 4a with unsymmetrical ketones. Cis-gamma-lactones can be converted into their trans-isomers by treatment with NaOEt in EtOH.