Iron-Catalyzed C2-C3 Bond Cleavage of Phenylpyruvate with O2: Insight into Aliphatic C-C Bond-Cleaving Dioxygenases

Paine, T.K., England, Jason and Que Jr., L. (2007) Iron-Catalyzed C2-C3 Bond Cleavage of Phenylpyruvate with O2: Insight into Aliphatic C-C Bond-Cleaving Dioxygenases. Chemistry - A European Journal, 13 (21). pp. 6073-6081. ISSN 0947-6539

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Iron(II)-phenylpyruvate complexes of tetradentate tris(6-methyl-2-pyridylmethyl)amine (6-Me3-TPA) and tridentate benzyl bis(2-quinolinylmethyl)amine (Bn-BQA) were prepared to gain insight into C-C bond cleavage catalyzed by dioxygenase enzymes. The complexes we have prepared and characterized are [Fe(6-Me3-tpa)(prv)][BPh4] (1), [Fe2(6-Me3-tpa)2(pp)][(BPh4)2] (2), and [Fe2(6-Me3-tpa)2(2′-NO2-pp)][(BPh4)2] (3), [Fe(6-Me3-tpa)(pp-Me)][BPh4] (4), [Fe(6-Me3-tpa)(CN-pp-Et)][BPh4] (5), and [Fe(Bn-bqa)(pp)] (8), in which PRV is pyruvate, PP is the enolate form of phenylpyruvate, 2′-NO2-PP is the enolate form of 2′-nitrophenylpyruvate, PP-Me is the enolate form of methyl phenylpyruvate, and CN-PP-Et is the enolate form of ethyl-3-cyanophenylpyruvate. The structures of mononuclear complexes 1 and 5 were determined by single-crystal X-ray diffraction. Both the PRV ligand in 1 and the CN-PP-Et ligand in 5 bind to the iron(II) center in a bidentate manner and form 5-membered chelate rings, but the α-keto moiety is in the enolate form in 5 with concomitant loss of a C-Hβ proton. The PP ligands of 2, 3, 4, and 8 react with dioxygen to form benzaldehyde and oxalate products, which indicates that the C2-C3 PP bond is cleaved, in contrast to cleavage of the C1C2 bond previously observed for complexes that do not contain α-ketocarboxylate ligands in the enolate form. These reactions serve as models for metal-containing dioxygenase enzymes that catalyze the cleavage of aliphatic C-C bonds.

Keywords:Amines, Carbon carbon composites, Chemical bonds, Complexation, Enzymes, Iron, Bioinorganic chemistry, C-C bond cleavage, Dioxygenase enzymes, Esters, acetonitrile, acetonitrile derivative, carbon, dioxygenase, iron, oxygen, phenylpyruvic acid, article, catalysis, chemical structure, chemistry, electrospray mass spectrometry, metabolism, oxidation reduction reaction, synthesis, X ray crystallography, Acetonitriles, Crystallography, X-Ray, Dioxygenases, Models, Molecular, Molecular Structure, Oxidation-Reduction, Phenylpyruvic Acids, Spectrometry, Mass, Electrospray Ionization
Subjects:F Physical Sciences > F120 Inorganic Chemistry
Divisions:College of Science > School of Chemistry
ID Code:51934
Deposited On:14 Oct 2022 12:37

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