Pyridyl Radical Cation for C−H Amination of Arenes

Electron‐transfer photocatalysis provides access to the elusive and unprecedented N‐pyridyl radical cation from selected N‐substituted pyridinium reagents. The resulting C(sp2)−H functionalization of (hetero)arenes furnishes versatile intermediates for the development of valuable aminated aryl scaff...

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Published inAngewandte Chemie Vol. 131; no. 2; pp. 536 - 541
Main Authors Rössler, Simon L., Jelier, Benson J., Tripet, Pascal F., Shemet, Andrej, Jeschke, Gunnar, Togni, Antonio, Carreira, Erick M.
Format Journal Article
LanguageEnglish
Published Weinheim Wiley Subscription Services, Inc 08.01.2019
Subjects
Amination
Aminierung
Aromatic compounds
Cations
Chemistry
Intermediates
Photoredox-Katalyse
Pyridinium
Pyridyl-Radikalkationen
Radikalischer Mechanismus
Reagents
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Summary:Electron‐transfer photocatalysis provides access to the elusive and unprecedented N‐pyridyl radical cation from selected N‐substituted pyridinium reagents. The resulting C(sp2)−H functionalization of (hetero)arenes furnishes versatile intermediates for the development of valuable aminated aryl scaffolds. Mechanistic studies that include the first spectroscopic evidence of a spin‐trapped N‐pyridyl radical adduct implicate SET‐triggered, pseudo‐mesolytic cleavage of the N−X pyridinium reagents mediated by visible light. Unbegangene Wege: Die Ein‐Elektronen‐Reduktion ausgewählter Pyridinium‐Reagentien führt über heterolytische Fragmentierung zu synthetisch nutzbaren N‐Pyridyl‐Radikalkationen. Diese reaktiven Intermediate wurden für die C‐H‐Aminierung von (Hetero)arenen zu N‐Arylpyridinium‐Verbindungen eingesetzt, wodurch verschiedene Stickstoff‐haltige Gerüste zugänglich werden.
Bibliography:These authors contributed equally to this work.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201810261