Mechanism of the Dehydrogenative Phenothiazination of Phenols

Chemistry : a European Journal
Monalisa GoswamiFrederic W Patureau

Abstract

The straightforward capture of oxidized phenothiazines with phenols under aerobic conditions represents a unique cross-dehydrogenative C-N bond-forming reaction in terms of operational simplicity. The mechanism of this cross-dehydrogenative N-arylation of phenothiazines with phenols has been the object of debate, particularly regarding the order in which the substrates are oxidized and their potentially radical or cationic nature. Understanding the selective reactivity of phenols for oxidized phenothiazines is one of the key objectives of this study. The reaction mechanism is investigated in detail by utilizing electron paramagnetic resonance spectroscopy, cyclic voltammetry, radical trap experiments, kinetic isotope effects, and solvent effects. Finally, the key reaction steps are calculated by using density functional theory (DFT) and broken-symmetry open-shell singlet DFT methods to unravel a unique biradical mechanism for the oxidative phenothiazination of phenols.

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Citations

Nov 8, 2018·Chemical Communications : Chem Comm·Luis BeringAndrey P Antonchick
Jan 17, 2020·Chemistry : a European Journal·Lukas M SigmundLutz Greb
Mar 3, 2020·Chemical Society Reviews·Congjun YuMónica H Pérez-Temprano
Dec 16, 2020·Angewandte Chemie·Christopher CremerFrederic W Patureau
Nov 17, 2020·Organic Letters·Christina L BubFrederic W Patureau
Apr 14, 2021·Organic Letters·Christopher CremerFrederic W Patureau
Aug 6, 2021·Chemical Communications : Chem Comm·Song ChenBin Tan
Aug 21, 2019·Organic Letters·Christian K RankFrederic W Patureau
Dec 4, 2019·Organic Letters·Pooja Y VemuriFrederic W Patureau
Aug 3, 2019·The Journal of Organic Chemistry·Claire EmpelRene M Koenigs

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Methods Mentioned

BETA
electron paramagnetic resonance
NMR
column chromatography

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