The oxidative cleavage of alkenes is an integral process that converts feedstock materials into high-value synthetic intermediates1,2,3. The most viable method to achieve this in one chemical step is with ozone4,5,6,7; however, this poses technical and safety challenges owing to the explosive nature of ozonolysis products8,9. Here we report an alternative approach to achieve oxidative cleavage of alkenes using nitroarenes and purple-light irradiation. We demonstrate that photoexcited nitroarenes are effective ozone surrogates that undergo facile radical [3+2] cycloaddition with alkenes. The resulting ‘N-doped’ ozonides are safe to handle and lead to the corresponding carbonyl products under mild hydrolytic conditions. These features enable the controlled cleavage of all types of alkenes in the presence of a broad array of commonly used organic functionalities. Furthermore, by harnessing electronic, steric and mediated polar effects, the structural and functional diversity of nitroarenes has provided a modular platform to obtain site selectivity in substrates containing more than one alkene.
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C(alkyl)–C(vinyl) bond cleavage enabled by Retro-Pallada-Diels-Alder reaction
Nature Communications Open Access 04 May 2023
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The data that support the findings of this study are available from the corresponding author (D.L.) upon reasonable request.
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D.L. thanks EPSRC for a Fellowship (EP/P004997/1) and a grant (EP/V046799/1), the European Research Council for a research grant (758427), the Leverhulme Trust for additional support (Philip Leverhulme Prize to D.L.). We acknowledge I. J. Vitorica-Yrezabal (University of Manchester) for solving the X-ray crystal structure of 4, and N. S. Sheikh for discussions.
The authors declare no competing interests.
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Ruffoni, A., Hampton, C., Simonetti, M. et al. Photoexcited nitroarenes for the oxidative cleavage of alkenes. Nature 610, 81–86 (2022). https://doi.org/10.1038/s41586-022-05211-0
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C(alkyl)–C(vinyl) bond cleavage enabled by Retro-Pallada-Diels-Alder reaction
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