Journal of Organic Chemistry p. 7957 - 7964 (1999)
Update date:2022-08-18
Topics:
Kanavarioti, Anastassia
Gangopadhyay, Sumana
Aqueous solutions of deoxyguanosine 5′-monophosphate 2-methylimidazolide, 2-MeImpdG, yield primarily deoxyguanosine 5′-monophosphate, 5′dGMP, and pyrophosphate-linked dideoxyguanylate, dG5′ppdG, abbreviated G2p (see Chart 1). The initial rate of G2p formation, d[G2p]/dt in M h-1, determined at 23°C, pH 7.8, 1.0 M NaCl and 0.2 M Mg2+ by timed high-performance liquid chromatography (HPLC) analysis, exhibits a second-order dependence on 2-MeImpdG concentration, [G]0, indicating a bimolecular mechanism of dimerization in the range 0.02 M ≤ [G]0 ≤ 0.09 M. In the presence of polycytidylate, poly(C), G2p synthesis is accelerated and oligodeoxyguanylate products are formed by incorporation of 2-MeImpdG molecules. The kinetics of G2p formation as a function of both monomer and polymer concentration, expressed in C equivalents, were also determined under the above conditions and exhibited a complex behavior. Specifically, at a constant [poly(C)], values of d[G2p]/dt typically increased with [G]0 with a parabolic upward curvature. At a constant [G]0, values of d[G2p]/dt increase with [poly(C)], but level off at the higher poly(C) concentrations. As [G]0 increases this saturation occurs at a higher poly(C) concentration, a result opposite to expectation for a simple complexation of two reacting monomers with the catalyst prior to reaction. Nevertheless, these results are shown to be quantitatively consistent with a template-directed (TD) mechanism of dimerization where poly(C) acts as the template to bind 2-MeImpdG in a cooperative manner and lead, for the first time, to the formulation of principles that govern template-directed chemistry. Analysis of the kinetic data via a proposed TD cooperative model provides association constants for the affinity between polymer and monomer and the intrinsic reactivity of 2-MeImpdG toward pyrophosphate synthesis. To the best of our knowledge, poly(C)/2-MeImpdG is the first system that could serve as a textbook example of a TD reaction under conditions such that the template is fully saturated by monomers and under conditions that it is not.
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