Journal of the American Chemical Society · 2017 · 105 citations · 22 references
Life SciencesBiochemistryMolecular BiologyBiocatalysisRna ProcessingSynthetic BiologyNucleic Acid SynthesisRibonucleic Acid (Rna) ChemistryChemical ActivationNucleobase FormationNucleotide Synthesis PathwaysPrebiotic Organic SynthesisPrebiotic Synthesis Of Amino AcidsPrebiotic Synthesis Of NucleotidesReaction Network SynthesisRibonucleotide Chemistry
We have recently shown that 2-aminoimidazole is a superior nucleotide activating group for nonenzymatic RNA copying. Here we describe a prebiotic synthesis of 2-aminoimidazole that shares a common mechanistic pathway with that of 2-aminooxazole, a previously described key intermediate in prebiotic nucleotide synthesis. In the presence of glycolaldehyde, cyanamide, phosphate and ammonium ion, both 2-aminoimidazole and 2-aminooxazole are produced, with higher concentrations of ammonium ion and acidic pH favoring the former. Given a 1:1 mixture of 2-aminoimidazole and 2-aminooxazole, glyceraldehyde preferentially reacts and cyclizes with the latter, forming a mixture of pentose aminooxazolines, and leaving free 2-aminoimidazole available for nucleotide activation. The common synthetic origin of 2-aminoimidazole and 2-aminooxazole and their distinct reactivities are suggestive of a reaction network that could lead to both the synthesis of RNA monomers and to their subsequent chemical activation.
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