The oxidation of a series of alkylaromatic compounds with H2O2 catalyzed by an imine-based non-heme iron complex prepared in situ by reaction of 2-picolylaldehyde, 2-picolylamine, and Fe(OTf)2 in a 2 : 2 : 1 ratio leads to a marked chemoselectivity for aromatic ring hydroxylation over side-chain oxidation. This selectivity is herein investigated in detail. Side-chain/ring oxygenated product ratio was found to increase upon decreasing the bond dissociation energy (BDE) of the benzylic C-H bond in line with expectation. Evidence for competitive reactions leading either to aromatic hydroxylation via electrophilic aromatic substitution or side-chain oxidation via benzylic hydrogen atom abstraction, promoted by a metal-based oxidant, has been provided by kinetic isotope effect analysis. This journal is

Insight into the chemoselective aromatic vs. side-chain hydroxylation of alkylaromatics with H2O2 catalyzed by a non-heme imine-based iron complex / Ticconi, B.; Capocasa, G.; Cerrato, A.; DI STEFANO, Stefano; Lapi, A.; Marincioni, B.; Olivo, G.; Lanzalunga, O.. - In: CATALYSIS SCIENCE & TECHNOLOGY. - ISSN 2044-4753. - 11:1(2021), pp. 171-178. [10.1039/d0cy01868f]

Insight into the chemoselective aromatic vs. side-chain hydroxylation of alkylaromatics with H2O2 catalyzed by a non-heme imine-based iron complex

Ticconi B.;Capocasa G.;Cerrato A.;Di Stefano S.;Lapi A.;Olivo G.;Lanzalunga O.
2021

Abstract

The oxidation of a series of alkylaromatic compounds with H2O2 catalyzed by an imine-based non-heme iron complex prepared in situ by reaction of 2-picolylaldehyde, 2-picolylamine, and Fe(OTf)2 in a 2 : 2 : 1 ratio leads to a marked chemoselectivity for aromatic ring hydroxylation over side-chain oxidation. This selectivity is herein investigated in detail. Side-chain/ring oxygenated product ratio was found to increase upon decreasing the bond dissociation energy (BDE) of the benzylic C-H bond in line with expectation. Evidence for competitive reactions leading either to aromatic hydroxylation via electrophilic aromatic substitution or side-chain oxidation via benzylic hydrogen atom abstraction, promoted by a metal-based oxidant, has been provided by kinetic isotope effect analysis. This journal is
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/1486200
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