The Kinetics and Mechanisms of Phosphoenolpyruvate Hydrolysis

S. J. Benkovic; K. J. Schray

doi:10.1021/bi00851a043

The Kinetics and Mechanisms of Phosphoenolpyruvate Hydrolysis

S. J. Benkovic, K. J. Schray

Chemistry

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40 Scopus citations

Abstract

The hydrolytic mechanisms of phosphoenolpyruvate and its reference compound ethyl phosphoenolpyruvate have been investigated. Rate constants for the protomeric species, activation energies, D₂O and nonaqueous solvent effects, and methyl phosphate- inorganic phosphate product distribution in methanol- H₂O solvent have led to the postulation of: (1) abnormally rapid phosphoenolpyruvate mono- and dianion and ethyl phosphoenolpyruvate monoanion hydrolysis via metaphosphate expulsion possibly involving a cyclic transition state, (2) unusual neutral species hydrolysis, (3) only small (3-40-fold) rate enhancement which was attributable to enol-ketone conversion energy, and (4) no demonstrable kinetically important role for the neighboring group of phosphoenolpyruvate.

Original language	English (US)
Pages (from-to)	4090-4096
Number of pages	7
Journal	Biochemistry
Volume	7
Issue number	11
DOIs	https://doi.org/10.1021/bi00851a043
State	Published - Nov 1 1968

All Science Journal Classification (ASJC) codes

Biochemistry

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10.1021/bi00851a043

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abstract = "The hydrolytic mechanisms of phosphoenolpyruvate and its reference compound ethyl phosphoenolpyruvate have been investigated. Rate constants for the protomeric species, activation energies, D2O and nonaqueous solvent effects, and methyl phosphate- inorganic phosphate product distribution in methanol- H2O solvent have led to the postulation of: (1) abnormally rapid phosphoenolpyruvate mono- and dianion and ethyl phosphoenolpyruvate monoanion hydrolysis via metaphosphate expulsion possibly involving a cyclic transition state, (2) unusual neutral species hydrolysis, (3) only small (3-40-fold) rate enhancement which was attributable to enol-ketone conversion energy, and (4) no demonstrable kinetically important role for the neighboring group of phosphoenolpyruvate.",

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AU - Benkovic, S. J.

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AB - The hydrolytic mechanisms of phosphoenolpyruvate and its reference compound ethyl phosphoenolpyruvate have been investigated. Rate constants for the protomeric species, activation energies, D2O and nonaqueous solvent effects, and methyl phosphate- inorganic phosphate product distribution in methanol- H2O solvent have led to the postulation of: (1) abnormally rapid phosphoenolpyruvate mono- and dianion and ethyl phosphoenolpyruvate monoanion hydrolysis via metaphosphate expulsion possibly involving a cyclic transition state, (2) unusual neutral species hydrolysis, (3) only small (3-40-fold) rate enhancement which was attributable to enol-ketone conversion energy, and (4) no demonstrable kinetically important role for the neighboring group of phosphoenolpyruvate.

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The Kinetics and Mechanisms of Phosphoenolpyruvate Hydrolysis

Abstract

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