title: Conversion of Aldehyde to Alkane by a Peroxoiron(III) Complex: A Functional Model for the Cyanobacterial Aldehyde-Deformylating Oxygenase.
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.
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, United States.
authors.forename: Alireza
authors.initials: A
authors.lastname: Shokri
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, United States.
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
mesh_terms: D000447:Aldehydes / Q000737:chemistry* / Q000378:metabolism; D000473:Alkanes / Q000737:chemistry* / Q000378:metabolism; D000458:Cyanobacteria / Q000737:chemistry / Q000201:enzymology*; D005227:Fatty Acids / Q000737:chemistry* / Q000378:metabolism; D005290:Ferric Compounds / Q000737:chemistry*; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry; D010105:Oxygenases / Q000737:chemistry / Q000378:metabolism*
chemical_list: D000447:Aldehydes; D000473:Alkanes; D005227:Fatty Acids; D005290:Ferric Compounds; C001634:fatty aldehyde; D010105:Oxygenases; D010100:Oxygen