Mechanisms and structures of crotonase superfamily enzymes--how nature controls enolate and oxyanion reactivity

Cell Mol Life Sci. 2008 Aug;65(16):2507-27. doi: 10.1007/s00018-008-8082-6.

Abstract

Structural and mechanistic studies on the crotonase superfamily (CS) are reviewed with the aim of illustrating how a conserved structural platform can enable catalysis of a very wide range of reactions. Many CS reactions have precedent in the 'carbonyl' chemistry of organic synthesis; they include alkene hydration/isomerization, aryl-halide dehalogenation, (de)carboxylation, CoA ester and peptide hydrolysis, fragmentation of beta-diketones and C-C bond formation, cleavage and oxidation. CS enzymes possess a canonical fold formed from repeated betabetaalpha units that assemble into two approximately perpendicular beta-sheets surrounded by alpha-helices. CS enzymes often, although not exclusively, oligomerize as trimers or dimers of trimers. Two conserved backbone NH groups in CS active sites form an oxyanion 'hole' that can stabilize enolate/oxyanion intermediates. The range and efficiency of known CS-catalyzed reactions coupled to their common structural platforms suggest that CS variants may have widespread utility in biocatalysis.

Publication types

  • Research Support, Non-U.S. Gov't
  • Review

MeSH terms

  • Amino Acid Sequence
  • Animals
  • Binding Sites
  • Carboxylic Acids / metabolism*
  • Enoyl-CoA Hydratase / chemistry*
  • Enoyl-CoA Hydratase / metabolism*
  • Humans
  • Molecular Sequence Data
  • Nature*
  • Protein Structure, Quaternary
  • Protein Structure, Secondary

Substances

  • Carboxylic Acids
  • Enoyl-CoA Hydratase