Inhibition of mandelate racemase by alpha-fluorobenzylphosphonates

Bioorg Med Chem Lett. 2003 Jun 16;13(12):2041-4. doi: 10.1016/s0960-894x(03)00311-1.

Abstract

Mandelate racemase catalyzes the interconversion of the enantiomers of mandelic acid. The enzyme binds the intermediate analogues (R)- and (S)-alpha-fluorobenzylphosphonate, and alpha,alpha-difluorobenzylphosphonate with 100-2500 times less affinity than it exhibits for (R,S)-alpha-hydroxybenzylphosphonate at pH 7.5. This apparent low affinity, relative to that of alpha-hydroxybenzylphosphonate, arises from the altered pKa values of the alpha-fluorobenzylphosphonates. For example, (S)-alpha-fluorobenzylphosphonate is bound with the same affinity as the substrate at pH 7.5, but this affinity is increased approximately 6-fold at pH 6.3.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Benzyl Compounds / chemistry
  • Benzyl Compounds / pharmacology
  • Enzyme Inhibitors / chemistry
  • Enzyme Inhibitors / pharmacology
  • Hydrocarbons, Fluorinated / chemistry*
  • Hydrocarbons, Fluorinated / pharmacology*
  • Hydrogen Bonding
  • Hydrogen-Ion Concentration
  • Kinetics
  • Magnesium / chemistry
  • Mandelic Acids / metabolism
  • Organophosphonates / chemistry*
  • Organophosphonates / pharmacology*
  • Pseudomonas putida / enzymology
  • Racemases and Epimerases / antagonists & inhibitors*
  • Racemases and Epimerases / metabolism
  • Recombinant Proteins / antagonists & inhibitors
  • Recombinant Proteins / metabolism
  • Stereoisomerism
  • Structure-Activity Relationship
  • Thermodynamics

Substances

  • Benzyl Compounds
  • Enzyme Inhibitors
  • Hydrocarbons, Fluorinated
  • Mandelic Acids
  • Organophosphonates
  • Recombinant Proteins
  • Racemases and Epimerases
  • mandelate racemase
  • Magnesium
  • mandelic acid