title: Adenine synthesis in interstellar space: mechanisms of prebiotic pyrimidine-ring formation of monocyclic HCN-pentamers.
abstract: The question whether the nucleobases can be synthesized in interstellar space is of fundamental significance in considerations of the origin of life. Adenine is formally the HCN pentamer, and experiments have demonstrated that adenine is formed under certain conditions by HCN pentamerization in gas, liquid, and condensed phases. Most mechanistic proposals invoke the intermediacy of the HCN tetramer AICN (4), and it is thought that adenine synthesis is completed by addition of the 5(th) HCN to 4 to form amidine 5 and subsequent pyrimidine cyclization. In this context, we have been studying the mechanism for prebiotic pyrimidine-ring formation of monocyclic HCN-pentamers with ab initio electronic structure theory. The calculations model gas phase chemistry, and the results primarily inform discussions of adenine synthesis in interstellar space. Purine formation requires tautomerization of 5 to the conjugated amidine 6 (via hydrogen-tunneling, thermally with H(+) -catalysis, or by photolysis) or to keteneimine 7 (by photolysis). It was found that 5-(N'-formamidinyl)-1H-imidazole-4-carbonitrile (6) can serve as a substrate for proton-catalyzed purine formation under photolytic conditions and N-(4-(iminomethylene)-1H-imidazol-5(4H)-ylidene)formamidine (7) can serve as a substrate for uncatalyzed purine formation under photolytic conditions. The absence of any sizeable activation barrier for the cyclization of 7 to the (Z)-imino form of 9H-adenine (Z)-2 is quite remarkable, and it is this feature that allows for the formation of the purine skeleton from 7 without any further activation.
authors.affiliation: Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211, USA. glaserr@missouri.edu
authors.forename: Rainer
authors.initials: R
authors.lastname: Glaser
authors.forename: Brian
authors.initials: B
authors.lastname: Hodgen
authors.forename: Dean
authors.initials: D
authors.lastname: Farrelly
authors.forename: Elliot
authors.initials: E
authors.lastname: McKee
mesh_terms: D000225:Adenine / Q000138:chemical synthesis* / Q000737:chemistry; D018559:Exobiology; D005118:Extraterrestrial Environment / Q000737:chemistry*; D008956:Models, Chemical; D000069497:Origin of Life; D011522:Protons; D013816:Thermodynamics
chemical_list: D011522:Protons; D000225:Adenine