Communication
Organic & Biomolecular Chemistry
Scheme 6 Proposed reaction mechanism.
compared to other ipso nitrations, an intramolecular nitro
transfer along with a radical pathway seems logical for the
reaction to proceed.
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Based on these experimental facts and reasoning, it could
be proposed that organoboronic acids in the presence of NBS
and PIFA generate O-centred radicals which react readily
with the nitro radical, generated through one electron oxi-
dation of NaNO2 in the presence of PIFA, to form the meta-
stable species I. Finally the nitroarenes are produced via nitro
transfer to the aryl moiety through 1,3-aryl migration from the
tetra-coordinated ‘ate’ species II which is most probably
formed from I through coordination by the succinimide
(Scheme 6).
In conclusion, we have developed a novel method for ipso
nitration of organoboronic acids using a combination of PIFA–
NBS and NaNO2. The method is applicable for aryl-, hetero-
aryl-, and alkylboronic acids and provides nitro compounds at
ambient temperature in a significantly less reaction time exhi-
biting a wide range of functional group tolerance. In this
context, it could be mentioned that the chemistry associated
with the reaction pathway of this nitration reaction could be
utilized in future for different functional group transform-
ations of the organoboronic acids. The simplicity, high
efficiency, use of easily available inexpensive reagents and also
the chemistry associated with it are the salient features of this
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Acknowledgements
We are grateful to CSIR, New Delhi, India for their generous
financial support and IIT Ropar for infrastructural facilities.
NC and DB would like to thank IIT Ropar and UGC, New
Delhi, respectively, for their fellowship.
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