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Therefore, although 6 has been demonstrated to play a key role
in reactions performed in organic solvents, it is only margin-
ally involved when H2O is used. In the proposed mechanism,
both 10 and 5 are believed to be the active oxidant species.
The reaction of aniline with 5 or 10 affords the hydroxylamine
11, which is further oxidised to dihydroxylamine 12 upon reac-
tion with a second equivalent of oxidant 5 or 10. In both these
steps, benzeneseleninic acid 4 is regenerated. The dihydroxyla-
mine 12 reasonably undergoes water elimination to afford
nitrosoarene 13 through a benzeneseleninic acid-mediated
proton transfer process. In the final step of the cycle, nitrosoar-
ene 13 reacts with 5 to provide nitroarene 1 and benzeneseleni-
nic acid 4.
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Conclusions
In conclusion, we have reported an unprecedented selenium-
catalysed methodology for the oxidation of anilines under
mild on water conditions. Mechanistically, the formation of
nitroarenes involves only Se(IV) active oxidant species.
Evidence suggestive of the exclusion of Se(VI) derivatives from
the catalytic cycle was provided by 77Se NMR studies and
mechanistic analyses.
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Conflicts of interest
There are no conflicts to declare.
13 For reviews on selenium-catalysed thiol-disulfide intercon-
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Acknowledgements
We thank MIUR, Italy (“Progetto Dipartimenti di Eccellenza
2018–2022” allocated to the Department of Chemistry “Ugo
Schiff”).
Notes and references
1 For books, see: (a) E. J. Lenardão, C. Santi and
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2 G. Franz and R. A. Sheldon, in Ullman’s Encyclopedia of
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I. W. C. E. Arends and R. A. Sheldon, J. Chem. Soc., Perkin 15 D. Zhao, M. Johansson and J.-E. Bäckvall, Eur. J. Org.
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