A novel nitration product formed during the reaction of peroxynitrite with 2′,3′,5′-tri-O-acetyl-7,8-dihydro-8-oxoguanosine:: N-nitro-N′-[1-(2,3,5-tri-O-acetyl-β-D-erythro-pentofuranosyl)-2,4-dioxoimidazolidin-5-ylidene]guanidine

A novel nitration product, formed during the reaction of peroxynitrite with 2',3',5'-tri-O-acetyl-7,8-dihydro-8-oxoguanosine, has been characterized using a combination of UV/vis, CD, and NMR spectroscopy and mass spectrometry. This compound has been identified as N-nitro-N'-[1-(2,3,5-tri-O-acetyl-beta-D-erythro-pentofuranosyl)-2,4-dioxoimidazolidin-5-ylidene]guanidine (IV). Upon base hydrolysis, IV releases nitroguanidine (IVa) and an intermediate, 1-(2,3,5-tri-O-acetyl-beta-D-erythro-pentofuranosyl)-5-iminoimidazolidine-2,4-dione (IVb). This intermediate is ultimately hydrolyzed to the stable 3-(2,3,5 -tri-O-acetyl-beta-D-erythro-pentofuranosyl)oxaluric acid (IVc). IV can be reduced by sodium borohydride to a pair of stable diastereomers (IVred). The formation of this product is rationalized in terms of initial oxidation of 2',3',5'-tri-O-acetyl-7,8-dihydro-8-oxoguanosine to a quinonoid diimine intermediate, 3. Nucleophilic attack at C5 of 3 by peroxynitrite leads to formation of a C5-oxyl radical species, 5, which then undergoes a series of rearrangements to yield an ylidene radical, 7. Combination of this radical species with nitrogen dioxide results in the formation of product IV.