methyl 4-(1,3-dioxoisoindolin-2-yl)but-2-enoate | 54238-27-6

• 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: methyl 4-(1,3-dioxoisoindolin-2-yl)but-2-enoate
• 英文别名: methyl (2E)-4-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)-2-butenoate；methyl 4-(1,3-dioxoisoindol-2-yl)but-2-enoate
• CAS: 54238-27-6
• 化学式: C₁₃H₁₁NO₄
• 分子量: 245.235
• InChiKey: LLDZOOUNGYCZSH-UHFFFAOYSA-N

物化性质

• 熔点：
  100 °C
• 沸点：
  387.6±35.0 °C(Predicted)
• 密度：
  1.312±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  63.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 4-(1,3-dioxoisoindolin-2-yl)but-2-enoate 、 [二氟(苯硫基)甲基]三甲基硅烷 在 四丁基二氟三苯硅酸铵 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以55%的产率得到methyl 4-(1-(difluoro(phenylsulfanyl)methyl)-1-hydroxy-3-oxoisoindolin-2-yl)but-3-enoate
  参考文献：
  名称：

  Fluoride-Catalyzed Addition of PhSCF₂SiMe₃ to N-Substituted Cyclic Imides Followed by Radical Cyclization: General Synthetic Strategy of gem-Difluoromethylenated 1-Azabicyclic Compounds

  摘要：

  PhSCF2SiMe3 (1) was found, for the first time, to undergo fluoride-catalyzed nucleophilic difluoro-(phenylsulfanyl)methylation reaction to cyclic imides 2, affording the corresponding adducts 3 in moderate to good yields. Reductive cleavage of the phenylsulfanyl group of N-alkylated adducts 3 with Bu3SnH/AIBN yielded gem-difluoromethylated products 4. Under the same reduction conditions, N-alkenylated and N-alkynylated adducts 3 afforded the corresponding gem-difluoromethylenated 1-azabicyclic compounds 5 and 6 with trans stereoselectivity. These compounds were employed as precursors for preparing substituted gem-difluoromethylenated pyrrolizidinones and indolizidinones 7 and 8 by treatment with Et3SiH/BF3 center dot OEt2, and compounds 9 and 10 by nucleophilic displacement of the hydroxyl group, using organosilanes in the presence of BF3 center dot OEt2. The synthesis of highly substituted gem-difluoromethylenated pyrrolizidines 13 and 14 was also demonstrated.

  DOI：

  10.1021/jo802794u
• 作为产物：
  描述：

  甲醇 、 N-丙炔基邻苯二甲酸胺 、 一氧化碳 在 1,5-bis(tert-butyl(pyridin-2-yl)phosphanyl)pentane 、 palladium(II) acetylacetonate 、 对甲苯磺酸 作用下， 80.0 ℃ 、4.0 MPa 条件下， 反应 20.0h， 以70%的产率得到methyl 2-((1,3-dioxoisoindolin-2-yl)methyl)acrylate
  参考文献：
  名称：

  炔烃的选择性钯催化羰基化：1,2-二羧酸二酯的原子经济合成

  摘要：

  首次设计合成了一类带有吡啶取代基的新型二膦配体。所得的 L1 钯配合物允许对各种芳香族和脂肪族炔烃进行化学和区域选择性二烷氧基羰基化，以高产率和选择性提供范围广泛的 1,4-二羧酸二酯。动力学研究表明通过相应炔烃的级联加氢酯化生成 1,4-二羧酸二酯。基于这些研究，炔烃羰基化的化学和区域选择性可以通过将配体从 L1 切换到 L3 或 L9 以得到 α,β-不饱和酯来控制。

  DOI：

  10.1021/jacs.8b05852

文献信息

• Selective Palladium-Catalyzed Carbonylation of Alkynes: An Atom-Economic Synthesis of 1,4-Dicarboxylic Acid Diesters
  作者：Jiawang Liu、Kaiwu Dong、Robert Franke、Helfried Neumann、Ralf Jackstell、Matthias Beller

  DOI：10.1021/jacs.8b05852

  日期：2018.8.15

  dialkoxycarbonylation of various aromatic and aliphatic alkynes affording a wide range of 1,4-dicarboxylic acid diesters in high yields and selectivities. Kinetic studies suggest the generation of 1,4-dicarboxylic acid diesters via cascade hydroesterification of the corresponding alkynes. Based on these investigations, the chemo- and regioselectivities of alkyne carbonylations can be controlled as shown by switching

  首次设计合成了一类带有吡啶取代基的新型二膦配体。所得的 L1 钯配合物允许对各种芳香族和脂肪族炔烃进行化学和区域选择性二烷氧基羰基化，以高产率和选择性提供范围广泛的 1,4-二羧酸二酯。动力学研究表明通过相应炔烃的级联加氢酯化生成 1,4-二羧酸二酯。基于这些研究，炔烃羰基化的化学和区域选择性可以通过将配体从 L1 切换到 L3 或 L9 以得到 α,β-不饱和酯来控制。
• Fluoride-Catalyzed Addition of PhSCF₂SiMe₃ to <i>N</i>-Substituted Cyclic Imides Followed by Radical Cyclization: General Synthetic Strategy of <i>gem</i>-Difluoromethylenated 1-Azabicyclic Compounds
  作者：Teerawut Bootwicha、Duanghathai Panichakul、Chutima Kuhakarn、Samran Prabpai、Palangpon Kongsaeree、Patoomratana Tuchinda、Vichai Reutrakul、Manat Pohmakotr

  DOI：10.1021/jo802794u

  日期：2009.5.15

  PhSCF2SiMe3 (1) was found, for the first time, to undergo fluoride-catalyzed nucleophilic difluoro-(phenylsulfanyl)methylation reaction to cyclic imides 2, affording the corresponding adducts 3 in moderate to good yields. Reductive cleavage of the phenylsulfanyl group of N-alkylated adducts 3 with Bu3SnH/AIBN yielded gem-difluoromethylated products 4. Under the same reduction conditions, N-alkenylated and N-alkynylated adducts 3 afforded the corresponding gem-difluoromethylenated 1-azabicyclic compounds 5 and 6 with trans stereoselectivity. These compounds were employed as precursors for preparing substituted gem-difluoromethylenated pyrrolizidinones and indolizidinones 7 and 8 by treatment with Et3SiH/BF3 center dot OEt2, and compounds 9 and 10 by nucleophilic displacement of the hydroxyl group, using organosilanes in the presence of BF3 center dot OEt2. The synthesis of highly substituted gem-difluoromethylenated pyrrolizidines 13 and 14 was also demonstrated.