Stoichiometric Aldehyde Deformylation Mediated by Nucleophilic Peroxo-diiron(III) Complex as a Functional Model of Aldehyde Deformylating Oxygenase

Chemistry. 2019 Nov 13;25(63):14290-14294. doi: 10.1002/chem.201903727. Epub 2019 Oct 15.

Abstract

The reactivity of the previously reported peroxo adduct [FeIII 2 (μ-O2 )(MeBzim-Py)4 (CH3 CN)2 ]4+ (1) (MeBzim-Py=2-(2'-pyridyl)-N-methylbenzimidazole) towards aldehyde substrates including phenylacetaldehyde (PAA), hydrocinnamaldehyde (HCA), propionaldehyde (PA), 2-phenylpropionaldehyde (PPA), cyclohexanecarboxaldehyde (CCA), and para-substituted benzaldehydes (benzoyl chlorides) has been investigated. Complex 1 proved to be a nucleophilic oxidant in aldehyde deformylation reaction. These models, including detailed kinetic and mechanistic studies, may serve as the first biomimics of aldehyde deformylating oxygenase (ADO) enzymes.

Keywords: Baeyer-Villiger reaction; aldehyde deformylating oxygenase; aldehyde deformylation; nucleophilic reactivity; μ-peroxo-FeIIIFeIII.

MeSH terms

  • Aldehydes / chemistry*
  • Biomimetic Materials / chemistry*
  • Biomimetic Materials / metabolism
  • Coordination Complexes / chemistry*
  • Coordination Complexes / metabolism
  • Ferric Compounds / chemistry*
  • Kinetics
  • Oxygenases / chemistry
  • Oxygenases / metabolism

Substances

  • Aldehydes
  • Coordination Complexes
  • Ferric Compounds
  • Oxygenases

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