Alternative bases in the RNA world:  the prebiotic synthesis of urazole and its ribosides.
Urazole is a five-membered heterocyclic compound which is isosteric with uracil's hydrogen-bonding segment.  Urazole reacts spontaneoulsy with ribose (and other aldoses) to give a mixture of four ribosides: alpha and beta pyranosides and furanosides.  This reaction occurs in aqueous solution at mild temperatures.  Thermodynamic and kinetic parameters for the reaction of urazole with ribose were determined.  In contrast, uracil is completely unreactive with ribose under these conditions.  Urazole's unusual reactivity is ascribed to the hydrazine portion of the molecule.  Urazole can be synthesized from biuret and hydrazine under prebiotic conditions.  The prebiotic synthesis of guanazole, which is isosteric in part to diaminopyrimidine and cytosine, is accomplished from dicyandiamide and hydrazine.  Kinetic parameters for both prebiotic reactions were measured.  Urazole and guanazole are transparent in the UV, which would be a favorable property in the absence of an ozone layer on the early Earth.  Urazole makes hydrogen bonds with adenine in DMSO similar to those of uracil, as established by H NMR.  All of these properties make urazole an attractive potential precursor to uracil and guanazole a potential precursor to cytosine in the RNA or pre-RNA world.
Kolb
V M
VM
Department of Chemistry, University of California, San Diego, La Jolla 92093-0317, USA.
Dworkin
J P
JP
Miller
S L
SL
D003596:Cytosine / Q000737:chemistry; D019418:Evolution, Chemical; D019143:Evolution, Molecular; D006144:Guanazole / Q000138:chemical synthesis* / Q000737:chemistry; D006834:Hydrazines / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D009705:Nucleosides / Q000138:chemical synthesis; D012313:RNA / Q000737:chemistry*; D012266:Ribose / Q000737:chemistry*; D014498:Uracil / Q000737:chemistry
D006834:Hydrazines; D009705:Nucleosides; D014498:Uracil; D012313:RNA; D012266:Ribose; D003596:Cytosine; D006144:Guanazole