Indigo dye production by enzymatic mimicking based on an iron(III)porphyrin

An overview of microbial indigo-forming enzymes

“…Moreover, their mammalian origin makes them hard to use in microbial fermentations. Inspired by the catalytic power of heme-dependent enzymes, chemical approaches are also explored in which bio-inspired catalysts are designed, based on the iron-porphyrin structure of heme cofactors (Rebelo et al 2014). This is a new approach to produce indigo based on a simple and cost-effective model system of the enzymes.…”

Biomimetic Oxidation of Benzofurans with Hydrogen Peroxide Catalyzed by Mn(III) Porphyrins

“…The possibility of modulating the metabolic activation of these enzymes using synthetic metalloporphyrins has been studied extensively in the last decades [5][6][7][8][9]. In this context, metalloporphyrins carrying electron-withdrawing moieties have succeeded in modelling CYPs active center that includes the iron complex of protoporphyrin IX (heme group) [10,11]. Efficient biomimetic approaches have advantages, as synthetic porphyrins are readily available and much easier to handle than the purified enzymes [7].…”

“…The oxidation of benzofuran (BF), 2-methylbenzofuran (2MBF), and 3-methylbenzofuran (3MBF) in the presence of an Fe(III) porphyrin and hydrogen peroxide was recently reported by us, and afforded a one-pot, green, and versatile method for the synthesis of novel and biologically active compounds [28]. The significantly different reactivity observed for iron and manganese porphyrins has been ascribed to the formation of different catalytic intermediates [10,29]. Some Mn(III) porphyrins have been used with success as models of CYPs in the oxidation of aromatic compounds, leading mainly to arene oxide products [19,30].…”

“…When using H2O2 as the oxidant, the absence of a co-catalyst leads to inactivation of the biomimetic systems [31]. [10]; (c) mechanism proposed for the biomimetic generation of oxo-species, where the co-catalysts mimic the action of proton-donating amino acids from the P450 active site.…”

Binuclear copper(II) complexes discriminating epimeric glycosides and α- and β-glycosidic bonds in aqueous solution

“…[1] While much progress has been made in the synthesis and evaluation of selective catalysts mimicking such features,[2–6] most synthetic entities do not show sufficient diastereoselective or even chiral discrimination ability in aqueous solution. Man-made stereoselective catalysts for the discrimination of epimeric glycosides in aqueous solution or the selective hydrolysis of α - and β -glycosidic bonds are not known yet.…”