title: Toluene dioxygenase-catalyzed cis-dihydroxylation of benzo[b]thiophenes and benzo[b]furans: synthesis of benzo[b]thiophene 2,3-oxide.
abstract: Enzymatic cis-dihydroxylation of benzo[b]thiophene, benzo[b]furan and several methyl substituted derivatives was found to occur in both the carbocyclic and heterocyclic rings. Relative and absolute configurations and enantiopurities of the resulting dihydrodiols were determined. Hydrogenation of the alkene bond in carbocyclic cis-dihydrodiols and ring-opening epimerization/reduction reactions of heterocyclic cis/trans-dihydrodiols were also studied. The relatively stable heterocyclic dihydrodiols of benzo[b]thiophene and benzo[b]furan showed a strong preference for the trans configuration in aqueous solutions. The 2,3-dihydrodiol metabolite of benzo[b]thiophene was utilized as a precursor in the chemoenzymatic synthesis of the unstable arene oxide, benzo[b]thiophene 2,3-oxide.
authors.affiliation: School of Chemistry and Chemical Engineering, Queens University, Belfast, N Ireland. 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: Ian N
authors.initials: IN
authors.lastname: Brannigan
authors.forename: Timothy A
authors.initials: TA
authors.lastname: Evans
authors.forename: Simon A
authors.initials: SA
authors.lastname: Haughey
authors.forename: Brian T
authors.initials: BT
authors.lastname: McMurray
authors.forename: John F
authors.initials: JF
authors.lastname: Malone
authors.forename: Peter B A
authors.initials: PB
authors.lastname: McIntyre
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Stevenson
authors.forename: Christopher C R
authors.initials: CC
authors.lastname: Allen
mesh_terms: D001572:Benzofurans / Q000737:chemistry / Q000378:metabolism*; D055162:Biocatalysis; D018360:Crystallography, X-Ray; D006900:Hydroxylation; D008958:Models, Molecular; D015394:Molecular Structure; D010105:Oxygenases / Q000378:metabolism*; D013237:Stereoisomerism; D013876:Thiophenes / Q000737:chemistry / Q000378:metabolism*
chemical_list: D001572:Benzofurans; D013876:Thiophenes; C088015:benzothiophene; D010105:Oxygenases; C023172:toluene dioxygenase; C105430:benzofuran