Reaction Routes for Experimentally Observed Intermediates in the Prebiotic Formation of Nucleobases under High-Temperature Conditions

The prebiotic synthesis of nucleobases is of particular interest, given the experimental evidence that indicated formation of the nucleobases under abiotic conditions on the Early Earth under high-temperature conditions. Biomolecules have been formed under meteoritic impact scenarios that lead to high temperature and the generation of high energy. Free radical pathways for the formation of biomolecules are appropriate under these conditions. Density functional theory computations were used to study the free radical routes for the formation of nucleobases at the UB3LYP/6-311G­(d,p) level. We have found that both 5-aminoimidazole-4-carboxamide (AICA) and 5-(formylamino)­imidazole-4-carboxamide (fAICA) are formed first from formamide then the nucleobases are formed. Calculated results show the radical reaction routes of AICA as a precursor for guanine. Both hypoxanthine and xanthine are formed from radical pathways of fAICA. In addition, generation of imino-AICA and imino-fAICA has been shown for the first time to be needed for the production of adenine, purine, and isoguanine. Formation of hypoxanthine and adenine/purine from fAICA and imino-fAICA, respectively, is consistent with experiments performed nearly seven decades ago