Molecular mechanism of the oxidative cleavage of alkenes by photoexcited nitroarenes
The oxidative cleavage - of alkenes is a common transformation in - organic synthesis. However, conventional methods like ozonolysis and the Lemieux-Johnson reaction suffer from safety and selectivity - concerns. A new, safe, and selective photochemical method using photoexcited nitroarenes has rece...
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| Main Authors: | , , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
June 10, 2026
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| In: |
Journal of the American Chemical Society
Year: 2026, Volume: 148, Issue: 22, Pages: 22488-22503 |
| ISSN: | 1520-5126 |
| DOI: | 10.1021/jacs.5c22754 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/jacs.5c22754
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| Author Notes: | David Klaverkamp, Friederike Schneider, Lara Denninger, Lukas Rach, Jens Bredenbeck, Andreas Dreuw, and Peter Gilch |
| Summary: | The oxidative cleavage - of alkenes is a common transformation in - organic synthesis. However, conventional methods like ozonolysis and the Lemieux-Johnson reaction suffer from safety and selectivity - concerns. A new, safe, and selective photochemical method using photoexcited nitroarenes has recently been reported independently by Ruffoni et - al. [Nature 2022, 610 (7930), 81-86] and Wise et al. [J. Am. Chem. Soc. 2022, 144 (34), 15437-15442], - with a clear focus on synthetic applications. Here, steady-state UV/vis, - NMR, and IR, as well as femtosecond UV/vis and IR absorption spectroscopy, - along with quantum chemistry, are used to investigate its kinetics - and the involved intermediates. For a nitrobenzene/alkene pair (4-cyanonitrobenzene - and cyclooctene), reaction quantum yields and rate constants are determined - and analyzed with support from quantum chemistry. The photoreaction - is shown to proceed via the triplet state of the nitroarene. This - state is quenched with a bimolecular rate constant of 6 × 109 M-1 s-1 by the alkene. - A new species is formed, which we assign to a triplet biradical intermediate. - Only ∼10% of the quenching events result in product formation. - The additional loss channel is assigned to the decay of the intermediate - to the starting materials. The elimination of this loss channel could - significantly improve the efficiency of this reaction. |
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| Item Description: | Online veröffentlicht: 6. Mai 2026 Gesehen am 06.08.2026 |
| Physical Description: | Online Resource |
| ISSN: | 1520-5126 |
| DOI: | 10.1021/jacs.5c22754 |