The reactivity of adenosine 5′-O-(S-methyl-1-thiotriphosphate): a facile way of generating cyclo-diphosphate dianion

Abstract

Adenosine 5′-O-(S-methyl 1-thiotriphosphate)(1) hydrolyses in [¹⁸O] water to give adenosine 5′-O-(S-methyl thiophosphate)(2) and [¹⁸O]inorganic pyrophosphate (4) as the major products, together with [¹⁸O]inorganic tetraphosphate (5) as a minor product, each of which can be accommodated by a mechanism involving cyclo-diphosphate dianion (3) as an intermediate; the related reaction in anhydrous acetonitrile gives rise to a transient species tentatively assigned to the cyclo-diphosphate.