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

Author:
Shokri, Alireza, Que, Lawrence
Source:
Journal of the American Chemical Society 2015 v.137 no.24 pp. 7686-7691
ISSN:
1520-5126
Subject:
aldehydes, alkanes, chemical bonding, iron, models, oxygen, oxygenases
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 [Feᴵᴵᴵ(η²-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.
Agid:
5412746