ethyl 1-(difluoromethyl)-1-hydroxy-3-oxoisoindoline-2-carboxylate | 1152033-20-9

• 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: ethyl 1-(difluoromethyl)-1-hydroxy-3-oxoisoindoline-2-carboxylate
• 英文别名: Ethyl 1-(difluoromethyl)-1-hydroxy-3-oxoisoindole-2-carboxylate
• CAS: 1152033-20-9
• 化学式: C₁₂H₁₁F₂NO₄
• 分子量: 271.22
• InChiKey: NUCOKDDXTCLKOY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  66.8
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  ethyl 1-(difluoro(phenylsulfanyl)methyl)-1-hydroxy-3-oxo-isoindoline-2-carboxylate 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 反应 5.0h， 以78%的产率得到ethyl 1-(difluoromethyl)-1-hydroxy-3-oxoisoindoline-2-carboxylate
  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

文献信息

• 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.