Catalytic C–H Arylation of Unactivated C–H Bonds by Silylium Ion-Promoted C(sp2)–F Bond Activation

Silylium ions facilitate the catalytic direct cross-coupling of aryl fluorides with simple arenes and alkanes. This C–H arylation approach is initiated by silylium ion-mediated fluoride abstraction, which is followed by Friedel–Crafts or C–H insertion reactions of the resulting phenyl cation equivalents. An o -silyl group in the fluoroarene substrate is the key for selective intermolecular transformations, stabilizing the aryl cation intermediate and serving as an internal silylium ion precursor.