Mechanism of the Dehydrogenative Phenothiazination of Phenols

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 obj...

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Bibliographic Details
Published in:Chemistry : a European journal Vol. 24; no. 46; pp. 11936 - 11943
Main Authors: Goswami, Monalisa, Konkel, Alexander, Rahimi, Maryam, Louillat‐Habermeyer, Marie‐Laure, Kelm, Harald, Jin, Rongwei, de Bruin, Bas, Patureau, Frederic W.
Format: Journal Article
Language:English
Published: WEINHEIM Wiley 14.08.2018
Wiley Subscription Services, Inc
John Wiley and Sons Inc
Subjects:
Aerobic conditions
Chemistry
Chemistry, Multidisciplinary
click chemistry
cross dehydrogenative couplings
Dehydrogenation
Density functional theory
Electron paramagnetic resonance
homolytic aromatic substitution
oxidative amination
Phenols
Phenothiazines
Physical Sciences
radicals
Reaction mechanisms
Science & Technology
Spectroscopy
Substrates
radicals
C-N
ARYLATION
click chemistry
TRANSFER RADICAL POLYMERIZATION
cross dehydrogenative couplings
HYDROGEN-ATOM ABSTRACTIONS
homolytic aromatic substitution
FUNCTIONALIZATION
AMINATION
BOND-DISSOCIATION ENERGIES
oxidative amination
SUBSTITUTED PHENOLS
H BONDS
DERIVATIVES
ISSN:0947-6539, 1521-3765, 1521-3765
Online Access:Get full text
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Summary: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. Together in perfect harmony: The mechanism of the straightforward capture of oxidized phenothiazines with phenols is investigated by electron paramagnetic resonance spectroscopy, cyclic voltammetry, radical‐trapping experiments, kinetic isotope effects, and solvent effects. The key reaction steps are calculated by using 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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ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.201800730