title: Catalytic Mechanisms of Fe(II)- and 2-Oxoglutarate-dependent Oxygenases.
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.
authors.affiliation: Departments of Microbiology and Molecular Genetics, Michigan State University, East Lansing, Michigan 48824.
authors.forename: Salette
authors.initials: S
authors.lastname: Martinez
authors.affiliation: Departments of Microbiology and Molecular Genetics, Michigan State University, East Lansing, Michigan 48824; Departments of Biochemistry and Molecular Biology, Michigan State University, East Lansing, Michigan 48824. Electronic address: hausinge@msu.edu.
authors.forename: Robert P
authors.initials: RP
authors.lastname: Hausinger
mesh_terms: D001419:Bacteria / Q000201:enzymology / Q000235:genetics; D055162:Biocatalysis; D002262:Carboxy-Lyases / Q000235:genetics / Q000378:metabolism*; D003500:Cyclization; D049308:Dioxygenases / Q000235:genetics / Q000378:metabolism*; D015870:Gene Expression; D054879:Halogenation; D006801:Humans; D006900:Hydroxylation; D007501:Iron / Q000378:metabolism*; D007527:Isoenzymes / Q000235:genetics / Q000378:metabolism; D007656:Ketoglutaric Acids / Q000378:metabolism*; D008958:Models, Molecular; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D007527:Isoenzymes; D007656:Ketoglutaric Acids; D007501:Iron; D049308:Dioxygenases; D002262:Carboxy-Lyases
keywords: 2-oxoglutarate; desaturation; dioxygenase; enzyme mechanism; halogenase; hydroxylase; iron; metalloenzyme; ring-formation