最近,氟磺酰基(-SO2F)基团的引入吸引了相当大的研究兴趣,因为该部分通常可以在化学生物学和药物发现的背景下提供增强的活性和新功能。在这里,我们报道了1-氟氨磺酰吡啶(FSAP)盐的设计和合成,它可以作为氟氨磺酰基自由基的有效光氧化还原活性前体,并使各种(杂)芳烃的直接自由基C-H氟磺酰胺化成为可能。这种方法具有温和的条件,可见光,广泛的底物范围,良好的群体容忍度,等。,通过使用有机光催化剂,无金属协议也是可行的。Further,FSAP也可以通过1,2-双官能化应用于烯烃的自由基官能化,自由基远端迁移,串联自由基-极性交叉反应,等。此外,还证明了通过将这种自由基C-H氟磺酰胺化与随后的水解以及产物衍生化相结合,(杂)芳烃的正式C-H甲基胺化。
Recently, the introduction of fluorosulfonyl (-SO2F) groups have attracted considerable research interests, as this moiety could often afford enhanced activities and new functions in the context of chemical biology and drug discovery. Herein, we report the design and synthesis of 1-fluorosulfamoyl-pyridinium (FSAP) salts, which could serve as an effective photoredox-active precursor to fluorosulfamoyl radicals and enable the direct radical C-H fluorosulfonamidation of a variety of (hetero)arenes. This method features mild conditions, visible light, broad substrate scope, good group tolerance, etc., and a metal-free protocol is also viable by using organic photocatalysts. Further, FSAP can also be applied to the radical functionalization of alkenes via 1,2-difunctionalization, radical distal migration, tandem radical-polar crossover reactions, etc. In addition, a formal C-H methylamination of (hetero)arenes by combining this radical C-H fluorosulfonamidation with subsequent hydrolysis as well as product derivatization are also demonstrated.