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

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(eta(2)-O-2)(TMC)(+) (TMC = tetramethylcyclam) causes a similar transformation in the presence of a suitable H atom donor, thus serving as 2 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.