Catalytic Mechanisms of Fe(II)- and 2-Oxoglutarate-dependent Oxygenases

J Biol Chem. 2015 Aug 21;290(34):20702-20711. doi: 10.1074/jbc.R115.648691. Epub 2015 Jul 7.

Abstract

Mononuclear non-heme Fe(II)- and 2-oxoglutarate (2OG)-dependent oxygenases comprise a large family of enzymes that utilize an Fe(IV)-oxo intermediate to initiate diverse oxidative transformations with important biological roles. Here, four of the major types of Fe(II)/2OG-dependent reactions are detailed: hydroxylation, halogenation, ring formation, and desaturation. In addition, an atypical epimerization reaction is described. Studies identifying several key intermediates in catalysis are concisely summarized, and the proposed mechanisms are explained. In addition, a variety of other transformations catalyzed by selected family members are briefly described to further highlight the chemical versatility of these enzymes.

Keywords: 2-oxoglutarate; desaturation; dioxygenase; enzyme mechanism; halogenase; hydroxylase; iron; metalloenzyme; ring-formation.

Publication types

  • Research Support, N.I.H., Extramural
  • Review

MeSH terms

  • Bacteria / enzymology
  • Bacteria / genetics
  • Biocatalysis
  • Carboxy-Lyases / genetics
  • Carboxy-Lyases / metabolism*
  • Cyclization
  • Dioxygenases / genetics
  • Dioxygenases / metabolism*
  • Gene Expression
  • Halogenation
  • Humans
  • Hydroxylation
  • Iron / metabolism*
  • Isoenzymes / genetics
  • Isoenzymes / metabolism
  • Ketoglutaric Acids / metabolism*
  • Models, Molecular
  • Oxidation-Reduction
  • Stereoisomerism

Substances

  • Isoenzymes
  • Ketoglutaric Acids
  • Iron
  • Dioxygenases
  • Carboxy-Lyases

Associated data

  • PDB/1GY9
  • PDB/2FCT