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the differently protected o-phenylenediamine. o-Nitroanilides
are known to be potential precursors for reductive cyclization
to obtain 2-substituted benzimidazoles. 2-Amino-anilides can
also be accessed from the reduction of the nitro compounds
and later easily decorated with halogens by the Sandmayer
reaction.
In conclusion we have reported the discovery of a new
nitration protocol from a hitherto unreported concomitant
azidation−oxidation reaction that delivers a variety of nitro-
substituted anilides and sulfonamides. The copper-catalyzed
mononitration reaction involves a novel and efficient C−N
bond forming reaction via direct CAr−H functionalization. For
the first time, a nitro group has been installed in one step
directly onto an aryl carbon by in situ oxidation of an incipient
arylazide. An inexpensive copper catalyst and readily available
reagents effect the CAr−H nitration without the exclusion of air
or moisture, which highlights the operational simplicity of the
reaction. Further mechanistic investigations are underway in
our laboratory.
ASSOCIATED CONTENT
* Supporting Information
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S
The Supporting Information is available free of charge on the
(6) All optimization tables, competition studies, and substrates
(7) (a) Tang, C.; Jiao, N. J. Am. Chem. Soc. 2012, 134, 18924. For
unstable azides: (b) Lubriks, D.; Sokolovs, I.; Suna, E. J. Am. Chem.
Soc. 2012, 134, 15436.
1H and 13C NMR spectra of all new compounds and the
experimental procedures (PDF)
(8) (a) Duchek, J.; Vasella, A. Helv. Chim. Acta 2011, 94, 977.
(b) Xing, R. G.; Li, Y. N.; Liu, Q.; Meng, Q. Y.; Li, J.; Shen, X. X.; Liu,
Z.; Zhou, B.; Yao, X.; Liu, Z. L. Eur. J. Org. Chem. 2010, 2010, 6627.
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C.; Lee, B. J.; Spergel, S. H.; Mertzman, M. E.; Pitts, W. J.; La Cruz, T.
E.; Schmidt, M. A.; Darvatkar, N.; Natarajan, S. R.; Baran, P. S. Science
2015, 348, 886. (f) Arai, N.; Onodera, N.; Dekita, A.; Hori, J.;
Ohkuma, T. Tetrahedron Lett. 2015, 56, 3913.
AUTHOR INFORMATION
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Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
BV thanks the University Grant Commission (UGC), New
Delhi.
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REFERENCES
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