Synthesis and study of (Z)-3-chlorophosphoenolpyruvate.

(Z)-3-Chlorophosphoenolpyruvate has been synthesized by the reaction of 3,3-dichloropyruvic acid with trimethylphosphite, followed by deesterification. This compound is a competitive inhibitor of pyruvate kinase and phosphoenolpyruvate carboxylase. Pyruvate kinase is not inactivated upon prolonged incubation with the compound, but phosphoenolpyruvate carboxylase is slowly inactivated (t1/2 = 5 h). The compound is a substrate for both enzymes, being acted upon by pyruvate kinase approximately 0.1% as rapidly as phosphoenolpyruvate itself. In the case of phosphoenolpyruvate carboxylase, the compound is converted into a 3:1 mixture of chloropyruvate and chlorooxalacetate, at an overall rate that is about 25% the carboxylation rate for phosphoenolpyruvate.

[1]  M. O'Leary,et al.  Phosphoenol-3-bromopyruvate. A mechanism-based inhibitor of phosphoenolpyruvate carboxylase from maize. , 1982, The Journal of biological chemistry.

[2]  D. Gonzalez,et al.  Carboxylation and dephosphorylation of phosphoenol-3-fluoropyruvate by maize leaf phosphoenolpyruvate carboxylase. , 1988, The Biochemical journal.

[3]  P. Wirsching,et al.  (Z)-3-(fluoromethyl)phosphoenolpyruvate: synthesis and enzymatic studies. , 1988, Biochemistry.

[4]  T. Nowak,et al.  Stereospecificity of (E)- and (Z)-phosphoenol-alpha-ketobutyrate with chicken liver phosphoenolpyruvate carboxykinase and related phosphoenolpyruvate-utilizing enzymes. , 1982, Biochemistry.

[5]  G. L. Kenyon,et al.  Analogs of phosphoenolpyruvate. On the specificity of pyruvate kinase from rabbit muscle. , 1971, Biochemistry.

[6]  T. Nowak,et al.  Stereoselectivity of interaction of phosphoenolpyruvate analogues with various phosphoenolpyruvate-utilizing enzymes. , 1984, Biochemistry.

[7]  A. Iglesias,et al.  Higher plant phosphoenolpyruvate carboxylase , 1987 .

[8]  M. O'Leary,et al.  Synthesis and study of phosphoenolthiopyruvate. , 1988, Biochemistry.

[9]  M. O'Leary,et al.  Reaction of phosphoenolpyruvate carboxylase with (Z)-3-bromophosphoenolpyruvate and (Z)-3-fluorophosphoenolpyruvate , 1988 .

[10]  G. L. Kenyon,et al.  PEI-cellulose thin-layer chromatography. Product studies of the creatine kinase and pyruvate kinase reactions. , 1974, Analytical biochemistry.

[11]  M. O'Leary.  Phosphoenolpyruvate Carboxylase: An Enzymologist's View , 1982 .

[12]  P. Wirsching,et al.  1-Carboxyallenyl phosphate, an allenic analogue of phosphoenolpyruvate. , 1988, Biochemistry.

[13]  I. A. Rose,et al.  The proton transfer reactions of muscle pyruvate kinase. , 1972, The Journal of biological chemistry.

[14]  M. O'Leary,et al.  Kinetic and isotope effect studies of maize phosphoenolpyruvate carboxylase. , 1981, Biochemistry.

[15]  G. Whitesides,et al.  Laboratory-scale enzymic/chemical syntheses of D- and L-.beta.-chlorolactic acid and D- and L-potassium glycidate , 1982 .

[16]  D. Gonzalez,et al.  Identification of 2-enolbutyrate as the product of the reaction of maize leaf phosphoenolpyruvate carboxylase with (Z)- and (E)-2-phosphoenolbutyrate: evidence from NMR and kinetic measurements , 1988 .

[17]  G. L. Kenyon,et al.  Analogs of phosphoenolpyruvate. Substrate specificities of enolase and pyruvate kinase from rabbit muscle. , 1972, Biochemistry.

[18]  D. Davies.  The Central Role of Phosphoenolpyruvate in Plant Metabolism , 1979 .

[19]  M. Sekine,et al.  Silyl phosphites. Part 20. A facile synthesis of phosphoenolpyruvate and its analogue utilizing in situ generated trimethylsilyl bromide , 1982 .

[20]  T. Sugiyama,et al.  Purification and characterization of phosphoenolpyruvate carboxylase from maize leaves. , 1976, Plant physiology.

[21]  P. Wirsching,et al.  (E)-3-Cyanophosphoenolpyruvate, a new inhibitor of phosphoenolpyruvate-dependent enzymes. , 1985, Biochemistry.