Mechanism of the Dehydrogenative Phenothiazination of Phenols
| Autor: | Maryam Rahimi, Bas de Bruin, Marie-Laure Louillat-Habermeyer, Harald Kelm, Monalisa Goswami, Frederic W. Patureau, Alexander Konkel, Rongwei Jin |
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| Přispěvatelé: | Faculty of Science, Nature Inspired Transition Metal Catalysis (HIMS, FNWI) |
| Rok vydání: | 2018 |
| Předmět: |
Reaction mechanism
Full Paper 010405 organic chemistry Chemistry Dehydrogenative Couplings | Hot Paper Radical Organic Chemistry General Chemistry Full Papers homolytic aromatic substitution radicals 010402 general chemistry 01 natural sciences oxidative amination Catalysis 0104 chemical sciences Computational chemistry click chemistry Kinetic isotope effect cross dehydrogenative couplings Density functional theory Reactivity (chemistry) Singlet state Solvent effects Cyclic voltammetry |
| Zdroj: | Chemistry-A European Journal, 24(46), 11936-11943. Wiley-VCH Verlag Chemistry-A European Journal Chemistry (Weinheim an Der Bergstrasse, Germany) |
| ISSN: | 1521-3765 0947-6539 |
| DOI: | 10.1002/chem.201800730 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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