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Hydrolysis of phosphorylated pyridine

Another mode for metal ion catalysis of phosphoryl transfer is by complexation with a nucleophile of the form R-OH, thereby facilitating its deprotonation to form the more nucleophilic alkoxide or hydroxide. An example is the catalysis of the aqueous hydrolysis of phosphorylated pyridines by Mg(OH) +. 71 A rate enhancement of 104 was attributed to the greater nucleophilicity of the metal-bound hydroxide relative to water. A further rate enhancement of 102 was attributed to induced intramolecularity arising from interaction of the metal ion with both the hydroxide nucleophile and the nonbridge phosphoryl oxygens in the transition state.71... [Pg.128]

Herschlag, D., Jencks, W.P. Catalysis of the hydrolysis of phosphorylated pyridines by Mg(OH)L a possible model for enzymic phosphoryl transfer. Biochemistry 1990, 29(21), 5172-5179. [Pg.193]


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