Photoinduced Oxygen Transfer using Nitroarenes for the Anaerobic Cleavage of Alkenes

14 July 2022, Version 3
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Herein we report the anaerobic cleavage of alkenes into carbonyl compounds using nitroarenes as oxygen transfer reagents under visible light. This approach serves as a safe and practical alternative to mainstream oxidative cleavage protocols, such as ozonolysis and the Lemieux–Johnson reaction. A wide range of alkenes possessing oxidatively sensitive functionalities underwent anaerobic cleavage to generate carbonyl derivatives with high efficiency and regioselectivity. Mechanistic studies support that the transformation occurs via direct photoexcitation of the nitroarene followed by a non-stereospecific radical cycloaddition event with alkenes. This leads to 1,3,2- and 1,4,2-dioxazolidine intermediates that fragment to give the carbonyl products. A combination of radical clock experiments and in situ PhotoNMR spectroscopy revealed the identities of the key radical species and the putative aryl dioxazolidine intermediates, respectively.

Keywords

Nitroarenes
photochemistry
anaerobic
cleavage of alkenes
olefins
carbonyl

Supplementary materials

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Supporting Information
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Experimental details, optimization studies, characterization data, and NMR spectra.
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