Chemoenzymatic synthesis of monocyclic arene oxides and arene hydrates from substituted benzene substrates

Derek R. Boyd*, Narain D. Sharma, Vera Ljubez, Peter K. M. McGeehin, Paul J. Stevenson, Marine Blain, Christopher C. R. Allen

*Corresponding author for this work

Research output: Contribution to journalArticle

5 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)3020-3029
JournalOrganic and Biomolecular Chemistry
Volume11
Issue number18
DOIs
Publication statusPublished - 26 Mar 2013

Keywords

  • CYCLOHEXADIENE-TRANS-DIOLS
  • ENZYME-CATALYZED SYNTHESIS
  • MONOSUBSTITUTED BENZENES
  • NIH SHIFT
  • HYPERAROMATIC STABILIZATION
  • NAPHTHALENE DIOXYGENASE
  • VALENCE ISOMERIZATION
  • BIPHENYL DIOXYGENASE
  • DIHYDRODIOL ISOMERS
  • LIVER-MICROSOMES

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Biochemistry

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