The reactivity of triesters is discussed in the general context of phosphate transfer, as usually studied for the reactions of mono- and diesters. Systematic work has typically concentrated on the Linear Free Energy Relationships measuring the dependence of reactivity on the nucleophile and the leaving group, but new results indicate that it can depend equally strongly on the two non-leaving (sometimes known as spectator) groups. This conclusion is supported by first results from theoretical calculations: which also predict that a two-step mechanism can be favored over a concerted SN2(P) mechanism even for reactions involving leaving groups as good as p-nitrophenolate. This article is part of a Special Issue entitled: Chemistry and mechanism of phosphatases, diesterases and triesterases.
|Número de páginas
|Biochimica et Biophysica Acta - Proteins and Proteomics
|Publicada - ene. 2013
|Publicado de forma externa