Anaerobic Hydroxylation of C(sp3)–H Bonds Enabled by the Synergistic Nature of Photoexcited Nitroarenes

A photoexcited-nitroarene-mediated anaerobic C–H hydroxylation of aliphatic systems is reported. The success of this reaction is due to the bifunctional nature of the photoexcited nitroarene, which serves as the C–H bond activator and the oxygen atom source. Compared to previous methods, this approa...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2023-02, Vol.145 (5), p.2794-2799
Main Authors: Paolillo, Joshua M., Duke, Alana D., Gogarnoiu, Emma S., Wise, Dan E., Parasram, Marvin
Format: Article
Language:English
Subjects:
Communication
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Summary:A photoexcited-nitroarene-mediated anaerobic C–H hydroxylation of aliphatic systems is reported. The success of this reaction is due to the bifunctional nature of the photoexcited nitroarene, which serves as the C–H bond activator and the oxygen atom source. Compared to previous methods, this approach is cost- and atom-economical due to the commercial availability of the nitroarene, the sole mediator of the reaction. Because of the anaerobic conditions of the transformation, a noteworthy expansion in substrate scope can be obtained compared to prior reports. Mechanistic studies support that the photoexcited nitroarenes engage in successive hydrogen atom transfer and radical recombination events with hydrocarbons, leading to N-arylhydroxylamine ether intermediates. Spontaneous fragmentation of these intermediates leads to the key oxygen atom transfer products.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.2c13502