Photochemical C(<i>sp</i>²)−H Pyridination via Arene–Pyridinium Electron Donor–Acceptor Complexes

Abstract

This report describes the development of a photochemical method for C(sp² )-H pyridination that leverages the photoexcitation of electron donor-acceptor (EDA) complexes. Experimental and DFT studies show that black light (λ_max ≈350 nm) irradiation of solutions of protonated pyridines (acceptors) and aromatic C-H substrates (donors) results in single electron transfer to form aryl radical cation intermediates that can be trapped with pyridine nucleophiles under aerobic conditions. With some modification of the reaction conditions, this EDA activation mode is also effective for promoting the oxidatively triggered S_N Ar pyridination of aryl halides. Overall, this report represents an inexpensive and atom-economical approach to photochemical pyridination reactions that eliminates the requirement of an exogenous photocatalyst.