Mechanisms of Hydrolysis of Phosphate Ester Derivatives of Phosphoenolpyruvic Acid

Keith J. Schray, Stephen Benkovic

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

The hydrolytic mechanisms of dibenzylphosphoenolpyruvic acid (I), benzylphenylphosphonoenol-pyruvic acid (II), and monobenzylphosphoenolpyruvic acid (III) involve cyclization by the undissociated carboxyl function to expel primarily the thermodynamically unfavorable leaving group, benzyl alcohol (80-90%). Products arising from enolic oxygen-phosphorus bond cleavage comprise the remaining pathway (10-15%). The pH-rate profiles and product studies in aqueous and hydroxylamine solutions suggest pentacovalent phosphorus intermediacy and the rapid, reversible formation of acyclic acyl phosphate or phosphonate in the reactions of I and II. Ill also forms acyclic acyl phosphate but apparently not reversibly under the experimental conditions. Phosphoenolpyruvic acid also cyclizes to the corresponding five-membered cyclic phosphate under these conditions. Hydrolysis in H218O indicates that decomposition of the cyclic acyl intermediates occuss with water attack on phosphorus rather than carbon. A rationale is offered for the product composition resulting from hydrolysis and hydroxylaminolysis for I-III and the unusual catalytic efficiency of the carboxyl function.

Original languageEnglish (US)
Pages (from-to)2522-2529
Number of pages8
JournalJournal of the American Chemical Society
Volume93
Issue number10
DOIs
StatePublished - May 1 1971

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Phosphorus
Hydrolysis
Esters
Phosphates
Derivatives
Acids
Benzyl Alcohol
Organophosphonates
Hydroxylamine
Cyclization
Pyruvic Acid
Carbon
Oxygen
Decomposition
Alcohols
Water
Chemical analysis

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Schray, Keith J. ; Benkovic, Stephen. / Mechanisms of Hydrolysis of Phosphate Ester Derivatives of Phosphoenolpyruvic Acid. In: Journal of the American Chemical Society. 1971 ; Vol. 93, No. 10. pp. 2522-2529.
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abstract = "The hydrolytic mechanisms of dibenzylphosphoenolpyruvic acid (I), benzylphenylphosphonoenol-pyruvic acid (II), and monobenzylphosphoenolpyruvic acid (III) involve cyclization by the undissociated carboxyl function to expel primarily the thermodynamically unfavorable leaving group, benzyl alcohol (80-90{\%}). Products arising from enolic oxygen-phosphorus bond cleavage comprise the remaining pathway (10-15{\%}). The pH-rate profiles and product studies in aqueous and hydroxylamine solutions suggest pentacovalent phosphorus intermediacy and the rapid, reversible formation of acyclic acyl phosphate or phosphonate in the reactions of I and II. Ill also forms acyclic acyl phosphate but apparently not reversibly under the experimental conditions. Phosphoenolpyruvic acid also cyclizes to the corresponding five-membered cyclic phosphate under these conditions. Hydrolysis in H218O indicates that decomposition of the cyclic acyl intermediates occuss with water attack on phosphorus rather than carbon. A rationale is offered for the product composition resulting from hydrolysis and hydroxylaminolysis for I-III and the unusual catalytic efficiency of the carboxyl function.",
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Mechanisms of Hydrolysis of Phosphate Ester Derivatives of Phosphoenolpyruvic Acid. / Schray, Keith J.; Benkovic, Stephen.

In: Journal of the American Chemical Society, Vol. 93, No. 10, 01.05.1971, p. 2522-2529.

Research output: Contribution to journalArticle

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N2 - The hydrolytic mechanisms of dibenzylphosphoenolpyruvic acid (I), benzylphenylphosphonoenol-pyruvic acid (II), and monobenzylphosphoenolpyruvic acid (III) involve cyclization by the undissociated carboxyl function to expel primarily the thermodynamically unfavorable leaving group, benzyl alcohol (80-90%). Products arising from enolic oxygen-phosphorus bond cleavage comprise the remaining pathway (10-15%). The pH-rate profiles and product studies in aqueous and hydroxylamine solutions suggest pentacovalent phosphorus intermediacy and the rapid, reversible formation of acyclic acyl phosphate or phosphonate in the reactions of I and II. Ill also forms acyclic acyl phosphate but apparently not reversibly under the experimental conditions. Phosphoenolpyruvic acid also cyclizes to the corresponding five-membered cyclic phosphate under these conditions. Hydrolysis in H218O indicates that decomposition of the cyclic acyl intermediates occuss with water attack on phosphorus rather than carbon. A rationale is offered for the product composition resulting from hydrolysis and hydroxylaminolysis for I-III and the unusual catalytic efficiency of the carboxyl function.

AB - The hydrolytic mechanisms of dibenzylphosphoenolpyruvic acid (I), benzylphenylphosphonoenol-pyruvic acid (II), and monobenzylphosphoenolpyruvic acid (III) involve cyclization by the undissociated carboxyl function to expel primarily the thermodynamically unfavorable leaving group, benzyl alcohol (80-90%). Products arising from enolic oxygen-phosphorus bond cleavage comprise the remaining pathway (10-15%). The pH-rate profiles and product studies in aqueous and hydroxylamine solutions suggest pentacovalent phosphorus intermediacy and the rapid, reversible formation of acyclic acyl phosphate or phosphonate in the reactions of I and II. Ill also forms acyclic acyl phosphate but apparently not reversibly under the experimental conditions. Phosphoenolpyruvic acid also cyclizes to the corresponding five-membered cyclic phosphate under these conditions. Hydrolysis in H218O indicates that decomposition of the cyclic acyl intermediates occuss with water attack on phosphorus rather than carbon. A rationale is offered for the product composition resulting from hydrolysis and hydroxylaminolysis for I-III and the unusual catalytic efficiency of the carboxyl function.

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