Minisci-Type C–H Methylation and Silylation of Heteroarenes with Visible Light and <i>N</i> -Fluorobenzenesulfonimide

Herein, we report a photochemical C-H methylation and silylation of heteroarenes through the combination of visible light and <i>N</i>-fluorobenzenesulfonimide (NFSI). This practical method allows for the incorporation of a methyl or silyl group, produced from methanol and hydrosilane, into heteroarene architectures in a photocatalyst- and metal-free fashion. Mechanistic investigation suggests that the N-centered radical, generated from homolysis of the N-F bond in NFSI, plays a critical role by abstracting a hydrogen atom from a C-H or Si-H bond.