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Prebiotic Routes to Nucleosides: A Quantum Chemical Insight into the Energetics of the Multistep Reaction Pathways
Author(s) -
Šponer Judit E.,
Šponer Jiří,
FuentesCabrera Miguel
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201002057
Subject(s) - nucleobase , ribose , chemistry , exothermic reaction , cytosine , abiogenesis , endothermic process , prebiotic , nucleoside , computational chemistry , combinatorial chemistry , stereochemistry , dna , biochemistry , organic chemistry , biology , adsorption , enzyme , genetics
One of the most controversial questions of the RNA world theory is the formation of nucleosides through the reaction of nucleobases with ribose. The study presented herein discusses the thermodynamics of nucleoside formation under prebiotic conditions through the classical reaction route, which involves ribose and cytosine, as well as through the novel pathway suggested by Powner et al. [ Nature 2009 , 459 , 239–242]. Our computations show that, in contrast to the classical pathway, the route proposed by Powner et al. perfectly satisfies all conditions of a typical metabolic pathway that occurs in living organisms. In addition, we reveal the reasons that render the reaction of ribose with nucleobases endothermic and, thereby, less plausible under prebiotic conditions. We show that phosphates may play an indispensable role in the glycosylation of nucleobases by making this endothermic reaction step exothermic. In addition, we describe the catalytic role of phosphate anions in the formation of 2‐aminooxazole, which is one of the key steps of the synthetic route reported by Powner et al.