title: Chemoenzymatic synthesis of monocyclic arene oxides and arene hydrates from substituted benzene substrates.
abstract: Enantiopure cis-dihydrodiol bacterial metabolites of substituted benzene substrates were used as precursors, in a chemoenzymatic synthesis of the corresponding benzene oxides and of a substituted oxepine, via dihydrobenzene oxide intermediates. A rapid total racemization of the substituted benzene 2,3-oxides was found to have occurred, via their oxepine valence tautomers, in accord with predictions and theoretical calculations. Reduction of a substituted arene oxide to yield a racemic arene hydrate was observed. Arene hydrates have also been synthesised, in enantiopure form, from the corresponding dihydroarene oxide or trans-bromoacetate precursors. Biotransformation of one arene hydrate enantiomer resulted in a toluene-dioxygenase catalysed cis-dihydroxylation to yield a benzene cis-triol metabolite.
authors.affiliation: School of Chemistry and Chemical Engineering, Queen's University, Belfast BT9 5AG, UK. 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: Vera
authors.initials: V
authors.lastname: Ljubez
authors.forename: Peter K M
authors.initials: PK
authors.lastname: McGeehin
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Stevenson
authors.forename: Marine
authors.initials: M
authors.lastname: Blain
authors.forename: Christopher C R
authors.initials: CC
authors.lastname: Allen
mesh_terms: D001554:Benzene / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D010087:Oxides / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism; D014867:Water / Q000737:chemistry*
chemical_list: D010087:Oxides; D014867:Water; D001554:Benzene