Abstract
Knowledge of prebiotic nucleobase formation is important for understanding the origin of contemporary genetics. Observation of nucleobase precursor radicals in previous impact laser plasma simulations of the late heavy bombardment period (FerusProc. Natl. Acad. Sci. U.S.A.2015, 112, 657) points toward possible nucleobase formation through free-radical pathways. However, previously explored radical routes to nucleobase formation involve a large number of reaction steps, repetitive addition of precursors, and a number of chemical transformations. The possibility of competing side reactions under such conditions questions the feasibility of such pathways. In view of these shortcomings, the present work employs density functional theory to explore purine formation pathways through reaction of cyanamide and cyanoacetylene with radicals via a five-membered intermediate, 4-cyanoimidazole in the presence of ammonia. Our analysis reveals that the skeletal components of 4-cyanoimidazole can be solely obtained from cyanamide and cyanoacetylene via barrierless cyclization and a small number of reaction steps. In addition, the proposed mechanisms are characterized by a small number of precursors and low energy barriers and are thus likely feasible under extreme conditions on the prebiotic earth such as meteoritic impact during late heavy bombardment period. Overall, the present study underscores the importance of cyanamide and cyanoacetylene precursors in kinetically accessible routes to purine formation.