C4-Selective C–H Borylation of Pyridinium Derivatives Driven by Electron Donor–Acceptor Complexes

The photoinduced C4-selective C–H borylation of pyridines was achieved using electron donor–acceptor complexes derived from a Lewis base and N-amidopyridinium salts under external oxidant- and photocatalyst-free conditions. Notably, the nucleophilic character of phosphite-ligated boryl radicals enables addition of a radical to position C4 of pyridinium salts to afford C4-borylated heteroarenes that are otherwise difficult to obtain. This approach provides a versatile platform for the installation of both phosphite- and amine-coordinated boron groups on a series of pyridines under mild conditions, demonstrating excellent C4-positional selectivity for the pyridine scaffolds.