Conversion of Aldehyde to Alkane by a Peroxoiron(III) Complex: A Functional Model for the Cyanobacterial Aldehyde-Deformylating Oxygenase

J Am Chem Soc. 2015 Jun 24;137(24):7686-91. doi: 10.1021/jacs.5b01053. Epub 2015 Jun 10.

Abstract

Cyanobacterial aldehyde-deformylating oxygenase (cADO) converts long-chain fatty aldehydes to alkanes via a proposed diferric-peroxo intermediate that carries out the oxidative deformylation of the substrate. Herein, we report that the synthetic iron(III)-peroxo complex [Fe(III)(η(2)-O2)(TMC)](+) (TMC = tetramethylcyclam) causes a similar transformation in the presence of a suitable H atom donor, thus serving as a functional model for cADO. Mechanistic studies suggest that the H atom donor can intercept the incipient alkyl radical formed in the oxidative deformylation step in competition with the oxygen rebound step typically used by most oxygenases for forming C-O bonds.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Aldehydes / chemistry*
  • Aldehydes / metabolism
  • Alkanes / chemistry*
  • Alkanes / metabolism
  • Cyanobacteria / chemistry
  • Cyanobacteria / enzymology*
  • Fatty Acids / chemistry*
  • Fatty Acids / metabolism
  • Ferric Compounds / chemistry*
  • Models, Molecular
  • Oxygen / chemistry
  • Oxygenases / chemistry
  • Oxygenases / metabolism*

Substances

  • Aldehydes
  • Alkanes
  • Fatty Acids
  • Ferric Compounds
  • fatty aldehyde
  • Oxygenases
  • Oxygen