3-nitropyridine electrophiles yielded substitution products 5aa and 5ag in which the amination occurred para to the nitro. 3,5difluoronitrobenzene gave exclusively the ortho-amination product 5ah. In general, nitropyridines gave higher yields of the ONSH product compared to nitrobenzenes, amination occurred ortho to the nitro except for 3-nitropyridines, and in all cases shown above, the product isolated bore a nitro group, not the nitroso. We used the 1,2-nitroaniline motif to build highly functionalized heterobicycles in one step via a reductive condensation using sodium dithionite (Table ). A range of 3H-imidazo [4,5c]pyridines 7 were synthesized bearing a chloride at the 4-position that could serve as a handle for further SNAr, Suzuki, or Buchwald-Hartwig type functionalizations. Table . One-pot condensation of 1,2-nitroanilines 5 and aldehydes 6.