Journal of the American Chemical Society

Regioselective aliphatic carbon-carbon bond cleavage by a model system of relevance to iron-containing acireductone dioxygenase.

PMID 23214721


Mononuclear Fe(II) complexes ([(6-Ph(2)TPA)Fe(PhC(O)C(R)C(O)Ph)]X (3-X: R = OH, X = ClO(4) or OTf; 4: R = H, X = ClO(4))) supported by the 6-Ph(2)TPA chelate ligand (6-Ph(2)TPA = N,N-bis((6-phenyl-2-pyridyl)methyl)-N-(2-pyridylmethyl)amine) and containing a β-diketonate ligand bound via a six-membered chelate ring have been synthesized. The complexes have all been characterized by (1)H NMR, UV-vis, and infrared spectroscopy and variably by elemental analysis, mass spectrometry, and X-ray crystallography. Treatment of dry CH(3)CN solutions of 3-OTf with O(2) leads to oxidative cleavage of the C(1)-C(2) and C(2)-C(3) bonds of the acireductone via a dioxygenase reaction, leading to formation of carbon monoxide and 2 equiv of benzoic acid as well as two other products not derived from dioxygenase reactivity: 2-oxo-2-phenylethylbenzoate and benzil. Treatment of CH(3)CN/H(2)O solutions of 3-X with O(2) leads to the formation of an additional product, benzoylformic acid, indicative of the operation of a new reaction pathway in which only the C(1)-C(2) bond is cleaved. Mechanistic studies show that the change in regioselectivity is due to the hydration of a vicinal triketone intermediate in the presence of both an iron center and water. This is the first structural and functional model of relevance to iron-containing acireductone dioxygenase (Fe-ARD'), an enzyme in the methionine salvage pathway that catalyzes the regiospecific oxidation of 1,2-dihydroxy-3-oxo-(S)-methylthiopentene to form 2-oxo-4-methylthiobutyrate. Importantly, this model system is found to control the regioselectivity of aliphatic carbon-carbon bond cleavage by changes involving an intermediate in the reaction pathway, rather than by the binding mode of the substrate, as had been proposed in studies of acireductone enzymes.

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Phenylglyoxylic acid, purum, ≥98.0% (T)
Phenylglyoxylic acid, 97%