2-allyl-3-[difluoro(phenylsulfanyl)methyl]-3-hydroxyisoindolin-1-one | 1152032-90-0

• 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-allyl-3-[difluoro(phenylsulfanyl)methyl]-3-hydroxyisoindolin-1-one
• 英文别名: 3-[Difluoro(phenylsulfanyl)methyl]-3-hydroxy-2-prop-2-enylisoindol-1-one
• CAS: 1152032-90-0
• 化学式: C₁₈H₁₅F₂NO₂S
• 分子量: 347.385
• InChiKey: WDBYMBPHKNFREP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 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-allyl-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-9b-hydroxy-2-methyl-2,3-dihydro-1H-pyrrolo[2,1-a]isoindol-5(9bH)-one 、 1,1-difluoro-9b-hydroxy-2-methyl-2,3-dihydro-1H-pyrrolo[2,1-a]isoindol-5(9bH)-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-烯丙基邻苯二甲酰亚胺 、 二氟甲基苯硫醚 在 P₄-tBu 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以74%的产率得到2-allyl-3-[difluoro(phenylsulfanyl)methyl]-3-hydroxyisoindolin-1-one
  参考文献：
  名称：

  在磷腈作为碱的存在下，羰基化合物与 PhSCF2H 的亲核宝石-二氟（苯硫基）甲基化

  摘要：

  通过在 THF 中使用二氟（苯硫基）甲烷 (PhSCF2H) 和磷腈碱 P4-tBu，已经实现了羰基化合物的直接亲核二氟（苯硫基）甲基化。不可烯醇化的醛类和酮类是适合进行亲核钆-二氟（苯硫基）甲基化的底物，以良好的产率提供 α-gem-二氟甲基化加合物。此外，该方法也适用于环状酰亚胺和酸酐。

  DOI：

  10.1002/ejoc.201402162

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.
• Nucleophilic<i>gem</i>-Difluoro(phenylsulfanyl)methylation of Carbonyl Compounds with PhSCF₂H in the Presence of a Phosphazene as a Base
  作者：Teerachai Punirun、Darunee Soorukram、Chutima Kuhakarn、Vichai Reutrakul、Manat Pohmakotr

  DOI：10.1002/ejoc.201402162

  日期：2014.7

  Direct nucleophilic gem-difluoro(phenylsulfanyl)methylation of carbonyl compounds has been achieved by use of difluoro(phenylsulfanyl)methane (PhSCF2H) and the phosphazene base P4-tBu in THF. Non-enolizable aldehydes and ketones are suitable substrates to undergo nucleophilic gem-difluoro(phenylsulfanyl)methylation, providing α-gem-difluoromethylated adducts in good yields. In addition, this methodology

  通过在 THF 中使用二氟（苯硫基）甲烷 (PhSCF2H) 和磷腈碱 P4-tBu，已经实现了羰基化合物的直接亲核二氟（苯硫基）甲基化。不可烯醇化的醛类和酮类是适合进行亲核钆-二氟（苯硫基）甲基化的底物，以良好的产率提供 α-gem-二氟甲基化加合物。此外，该方法也适用于环状酰亚胺和酸酐。