Communication
ChemComm
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the reaction conditions (AcOH is formed), as suggested by Minisci
in his seminal studies on the addition of related formamide
(HC(QO)NH2) onto hereoarenes.4a,5b Such a protonation would
activate the heteroarene toward the addition of the electron-rich
carbamoyl radical to form N-protonated-IV. The ensuing loss of the
a-C–H as a proton would produce a rather stable allylic captodative
+
radical species, whose oxidation (by PCꢁ ) would give the final
protonated amide. This mechanism cannot be formally ruled out
at this stage, although our conditions are much less acidic than
those in Minisci’s work.4a,5b
In summary, we reported the addition onto heteroaromatic
bases, of carbamoyl radical species generated through a ‘‘metal-
free’’ photocatalyzed decarboxylation of oxamic acids. This
strategy allows a straightforward and environmentally benign
carbamoylation of a variety of N-heterocycles. The methodology
uses readily available starting material as well as standard
photocatalyst and organic oxidant sources. The reaction conditions
are mild, offering access to heteroaryl amides derived from amino-
acids without racemization.
AHJ thanks the Shaheed Benazir Bhutto University for a PhD
grant. We are grateful to the University of Bordeaux (UBx),
for the 2017 IdEx Bordeaux Post-doctoral Program, and to the
CNRS for financial support. We gratefully thank Dr D. M. Bassani
(UBx) for fluorescence experiments.
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Conflicts of interest
There are no conflicts to declare.
¨
B. Konig, Angew. Chem., Int. Ed., 2018, 57, 10034.
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