A stereoelectronic effect in prebiotic nucleotide synthesis.

ACS Chem Biol
Authors
Keywords
Abstract

A plausible route for the spontaneous synthesis of an activated ribonucleotide that is poised for polymerization has been put forth (Powner et al. (2009) Nature, 459, 239-242). A key step in this route necessitates the regioselective phosphorylation of the secondary alcohol on C(3') of an anhydroarabinonucleoside in the presence of the primary alcohol on C(5'). Here, we propose that this regioselectivity relies on electron delocalization between a lone pair (n) of O(5') and an antibonding orbital (pi*) of C(2) horizontal lineN(3). This n-->pi* interaction modulates reactivity without the use of a protecting group. Thus, a stereoelectronic effect could have opened a gateway to the "RNA world", the chemical milieu from which the first forms of life are thought to have emerged on Earth some 4 billion years ago.

Year of Publication
2010
Journal
ACS Chem Biol
Volume
5
Issue
7
Pages
655-7
Date Published
2010 Jul 16
ISSN
1554-8937
DOI
10.1021/cb100093g
PubMed ID
20499895
PubMed Central ID
PMC2912435
Links
Grant list
MC_UP_A024_1009 / Medical Research Council / United Kingdom
R01 AR044276 / AR / NIAMS NIH HHS / United States
R01 AR044276-15 / AR / NIAMS NIH HHS / United States