title: Dioxygenase-catalysed cis-dihydroxylation of meta-substituted phenols to yield cyclohexenone cis-diol and derived enantiopure cis-triol metabolites.
abstract: cis-Dihydroxylation of meta-substituted phenol (m-phenol) substrates, to yield the corresponding cyclohexenone cis-diol metabolites, was catalysed by arene dioxygenases present in mutant and recombinant bacterial strains. The presence of cyclohexenone cis-diol metabolites and several of their cyclohexene and cyclohexane cis-triol derivatives was detected by LC-TOFMS analysis and confirmed by NMR spectroscopy. Structural and stereochemical analyses of chiral ketodiol bioproducts, was carried out using NMR and CD spectroscopy and stereochemical correlation methods. The formation of enantiopure cyclohexenone cis-diol metabolites is discussed in the context of postulated binding interactions of the m-phenol substrates at the active site of toluene dioxygenase (TDO).
authors.affiliation: School of Chemistry and Chemical Engineering, Queen's University Belfast, Belfast, UK BT9 5AG. dr.boyd@qub.ac.uk
authors.forename: Derek R
authors.initials: DR
authors.lastname: Boyd
authors.forename: Narain D
authors.initials: ND
authors.lastname: Sharma
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Stevenson
authors.forename: Marine
authors.initials: M
authors.lastname: Blain
authors.forename: Colin
authors.initials: C
authors.lastname: McRoberts
authors.forename: John T G
authors.initials: JT
authors.lastname: Hamilton
authors.forename: José M
authors.initials: JM
authors.lastname: Argudo
authors.forename: Harpinder
authors.initials: H
authors.lastname: Mundi
authors.forename: Leonid A
authors.initials: LA
authors.lastname: Kulakov
authors.forename: Christopher C R
authors.initials: CC
authors.lastname: Allen
mesh_terms: D055162:Biocatalysis; D003511:Cyclohexanols / Q000737:chemistry* / Q000378:metabolism; D003512:Cyclohexanones / Q000737:chemistry* / Q000378:metabolism; D049308:Dioxygenases / Q000378:metabolism*; D006900:Hydroxylation; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010636:Phenols / Q000737:chemistry* / Q000378:metabolism; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D003511:Cyclohexanols; D003512:Cyclohexanones; D010636:Phenols; D049308:Dioxygenases