ChemComm
Communication
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Scheme 4 Proposed mechanism for nitration of aryl sulfonamides.
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presence of an oxidant, aryl sulfonamide 1 is oxidized to cation A,
which has another two resonance structures B and C. The nitro
anion attacks carbocation B or C to afford intermediate D and E,
which undergoes a re-aromatization step by deprotonation to give
product 2 or 20.
In conclusion, we have developed an efficient, convenient and
highly chemoselective method for the direct oxidative nitration of
aromatic sulfonamides with sodium nitrite as the nitrating reagent.
The mild conditions, good functional group compatibility, opera-
tional simplicity and high yield are expected to make this reaction
attractive to chemists. The reaction can also be scalable when
operated on a gram scale. Efforts toward detailed mechanistic
studies to understand the nitration process are underway.
We thank the National Science Foundation (NSF21072081,
21302076) and the National Basic Research Program of China
(973 Program) 2010CB8-33203 for financial support. We also
acknowledge support from the ‘‘111’’ Project and Program for
Changjiang Scholars, Innovative Research Team in University
(IRT1138), and the Fundamental Research Funds for the Central
Universities (lzujbky-2013-190, lzujbky-2014-194).
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