Stoichiometric Aldehyde Deformylation Mediated by Nucleophilic Peroxo‐diiron(III) Complex as a Functional Model of Aldehyde Deformylating Oxygenase. Issue 63 (15th October 2019)

• Record Type: Journal Article
• Authors: Kripli, Balázs; Csendes, Flóra Viktória; Török, Patrik; Speier, Gábor; Kaizer, József
• Is Part Of: Chemistry. Volume 25:Issue 63(2019)
• Page Start: 14290
• Page End: 14294
• Publication Date: 2019-10-15
• Subjects: aldehyde deformylating oxygenase -- aldehyde deformylation -- Baeyer–Villiger reaction -- nucleophilic reactivity -- μ-peroxo-FeIIIFeIII; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201903727
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The reactivity of the previously reported peroxo adduct [Fe III 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. Abstract : Aldehyde deformylation by μ‐peroxo‐diiron(III) : This study reports the first example for a well‐defined peroxo‐diiron(III) species to perform nucleophilic deformylation of various aldeydes, which is mechanistically akin to the oxidative deformylation of fatty aldehydes by aldehyde deformylating oxygenase (ADO) enzymes.