Photoredox-catalyzed aminofluorosulfonylation of unactivated olefins

• Published in: Chemical science (Cambridge) Vol. 12; no. 27; pp. 9359 - 9365
• Main Authors: Zhong, Tao, Yi, Ji-Tao, Chen, Zhi-Da, Zhuang, Quan-Can, Li, Yong-Zhao, Lu, Gui, Weng, Jiang
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 14-07-2021; The Royal Society of Chemistry
• Subjects: Alkenes; Chemical reactions; Chemical synthesis; Chemistry; Cross coupling; Electron transfer; Fluorides; Functional groups; Photoredox catalysis; Transition metals
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d1sc02503a

The development of efficient approaches to access sulfonyl fluorides is of great significance because of the widespread applications of these structural motifs in many areas, among which the emerging sulfur(
vi
) fluoride exchange (SuFEx) click chemistry is the most prominent. Here, we report the first three-component aminofluorosulfonylation of unactivated olefins by merging photoredox-catalyzed proton-coupled electron transfer (PCET) activation with radical relay processes. Various aliphatic sulfonyl fluorides featuring a privileged 5-membered heterocyclic core have been efficiently afforded under mild conditions with good functional group tolerance. The synthetic potential of the sulfonyl fluoride products has been examined by diverse transformations including SuFEx reactions and transition metal-catalyzed cross-coupling reactions. Mechanistic studies demonstrate that amidyl radicals, alkyl radicals and sulfonyl radicals are involved in this difunctionalization transformation.
A three-component aminofluorosulfonylation of unactivated alkenes has been developed by merging photocatalytic PCET with radical relay processes, affording various aliphatic sulfonyl fluorides featuring medicinally privileged heterocyclic scaffolds.