Activating Water: Important Effects of Non‐leaving Groups on the Hydrolysis of Phosphate Triesters
作者： Anthony J Kirby , Michelle Medeiros , Pedro SM Oliveira , Elisa S Orth , Tiago AS Brandão
关键词: Hydrolysis 、 Intramolecular force 、 Catalysis 、 Nucleophile 、 Aryl 、 Medicinal chemistry 、 Chemistry 、 Phosphate 、 Leaving group 、 Reactivity (chemistry) 、 Organic chemistry
摘要: The high rate of spontaneous hydrolysis tris-2-pyridyl phosphate (TPP) is explained by the activating effects non-leaving ("spectator") groups on P-OAr cleavage, and not intramolecular catalysis. Previous work phosphate-transfer reactions has concentrated contributions to reactivity nucleophile leaving group, but our results make clear that phosphorus can be equally significant. Rate measurements for three series triesters showed sensitivities are substantial reactions, although significantly smaller with good nucleophiles. There differences between triaryl dialkyl aryl in more reactive systems showing lower values both β(LG) β(NLG). Intramolecular catalysis TPP neighbouring pyridine nitrogens insignificant, primarily because their low basicity.
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