2-(but-3-enyl)-3-(difluoro(phenylsulfanyl)methyl)-3-hydroxyisoindolin-1-one | 1152033-10-7

• 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: 2-(but-3-enyl)-3-(difluoro(phenylsulfanyl)methyl)-3-hydroxyisoindolin-1-one
• 英文别名: 2-But-3-enyl-3-[difluoro(phenylsulfanyl)methyl]-3-hydroxyisoindol-1-one
• CAS: 1152033-10-7
• 化学式: C₁₉H₁₇F₂NO₂S
• 分子量: 361.412
• InChiKey: HPPJHGCPVCAZIJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  65.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-(but-3-enyl)-3-(difluoro(phenylsulfanyl)methyl)-3-hydroxyisoindolin-1-one 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， 生成 1,1-difluoro-10b-hydroxy-2-methyl-1,2,3,4-tetrahydropyrido[2,1-a]isoindol-6(10bH)-one 、 1,1-difluoro-10b-hydroxy-2-methyl-1,2,3,4-tetrahydropyrido[2,1-a]isoindol-6(10bH)-one
  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：

  N-(4-烯丁基)邻苯二甲酰亚胺 、 [二氟(苯硫基)甲基]三甲基硅烷 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以76%的产率得到2-(but-3-enyl)-3-(difluoro(phenylsulfanyl)methyl)-3-hydroxyisoindolin-1-one
  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