We report the catalytic generation of pyridyl radicals through photoexcitation of the electron donor-acceptor (EDA) complex, which enables the C2-selective heteroarylation of indole under ambient conditions. In this manifold, catalytic triarylamine and chloropyridine aggregate into an EDA complex in the presence of an inorganic base, making readily available chloropyridines good precursors for the generation of diverse pyridyl radicals. Given the broad reaction scope, this catalytic EDA complex protocol provides robust access to heterobiaryl scaffolds that are widely present in biologically important molecules.
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