(E)-ethyl 2-(3-oxoisoindolin-1-ylidene)acetate | 26191-41-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: (E)-ethyl 2-(3-oxoisoindolin-1-ylidene)acetate
• 英文别名: ethyl (E)-2-(3-oxoisoindolin-1-ylidene)acetate；seqtrans-3-Ethoxycarbonylmethylen-isoindolinon-1；trans-1-Ethoxycarbonylmethylen-isoindolon-3；ethyl (2E)-2-(3-oxoisoindol-1-ylidene)acetate
• CAS: 26191-41-3
• 化学式: C₁₂H₁₁NO₃
• 分子量: 217.224
• InChiKey: ISYSKHFFYFALKL-JXMROGBWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-ethyl 2-(3-oxoisoindolin-1-ylidene)acetate 在 三丁基膦 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以99%的产率得到(Z)-ethyl 2-(3-oxoisoindolin-1-ylidene)acetate
  参考文献：
  名称：

  Stereoselective Synthesis of 3-Methyleneisoindolin-1-ones via Base-Catalyzed Intermolecular Reactions of Electron-Deficient Alkynes with N-Hydroxyphthalimides

  摘要：

  Highly stereoselective intermolecular reactions of electron-deficient alkynes with N-hydroxyphthalimides for efficient construction of N-unprotected 3-methyleneisoindolin-1-ones have been developed through base catalytic strategies. The reaction of alkynoates with N-hydroxyphthalimides catalyzed by Bu3P in DMF at 150 degrees C gave the corresponding 3-methyleneisoindolin-1-ones with a (Z)-configuration, while the reaction of alkynoates with N-hydroxyphthalimides catalyzed by K2CO3 in DMF at 60 degrees C gave the corresponding 3-methyleneisoindolin-1-ones with an (E)-configuration, and (Z)-3-methyleneisoindolin-1-ones were obtained when alkyne ketones reacted with N-hydroxyphthalimide.

  DOI：

  10.1021/acs.joc.5b00002
• 作为产物：
  描述：

  3a-hydroxy-8-oxo-3a,8-dihydro-1-oxa-8a-azacyclopenta[a]indene-3-carboxylic acid ethyl ester 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 以83%的产率得到(E)-ethyl 2-(3-oxoisoindolin-1-ylidene)acetate
  参考文献：
  名称：

  Stereoselective Synthesis of 3-Methyleneisoindolin-1-ones via Base-Catalyzed Intermolecular Reactions of Electron-Deficient Alkynes with N-Hydroxyphthalimides

  摘要：

  Highly stereoselective intermolecular reactions of electron-deficient alkynes with N-hydroxyphthalimides for efficient construction of N-unprotected 3-methyleneisoindolin-1-ones have been developed through base catalytic strategies. The reaction of alkynoates with N-hydroxyphthalimides catalyzed by Bu3P in DMF at 150 degrees C gave the corresponding 3-methyleneisoindolin-1-ones with a (Z)-configuration, while the reaction of alkynoates with N-hydroxyphthalimides catalyzed by K2CO3 in DMF at 60 degrees C gave the corresponding 3-methyleneisoindolin-1-ones with an (E)-configuration, and (Z)-3-methyleneisoindolin-1-ones were obtained when alkyne ketones reacted with N-hydroxyphthalimide.

  DOI：

  10.1021/acs.joc.5b00002

文献信息

• Geometry Driven Intramolecular Oxidative Cyclization of Enamides: An Umpolung Annulation of Primary Benzamides with Acrylates for the Synthesis of 3-Methyleneisoindolin-1-ones
  作者：Joydev K. Laha、Mandeep Kaur Hunjan、Rohan A. Bhimpuria、Deepika Kathuria、Prasad V. Bharatam

  DOI：10.1021/acs.joc.7b00966

  日期：2017.7.21

  A palladium-catalyzed tandem oxidative annulation of primary benzamides with acrylates via intermolecular N-alkenylation followed by intramolecular C-alkenylation yielded a stereoselective synthesis of (E)-3-methyleneisoindolin-1-ones. The study unveils, for the first time, that only E-enamides could undergo intramolecular oxidative cyclization under the optimized conditions to give isoindolinones

  通过分子间的N-烯基化作用，然后通过分子内的C-烯基化作用，钯催化的苯甲酰胺与丙烯酸酯的串联氧化环化反应产生了（E）-3-亚甲基异吲哚啉-1-酮的立体选择性合成。该研究首次揭示，只有E-烯酰胺才能在优化条件下进行分子内氧化环化反应，得到异吲哚啉酮。与使用苯甲酰胺的文献方法相比，当前的策略代表了应有的策略。