Organic Letters
Letter
dicarbonate followed by hydrolysis of the resulting imidazolium
salt led to the cleavage of imidazole ring to provide
corresponding o-diamino arenes 22a and 22b with very good
yields. Nitro imidazole derivative 23 was obtained from the
reaction of 2 in the nitrating mixture. The bromo functionality of
Maulide, N. Chem. - Eur. J. 2013, 19, 13274. (d) Campos, K. R. Chem.
Soc. Rev. 2007, 36, 1069. (e) Doye, S. Angew. Chem., Int. Ed. 2001, 40,
3
351. For selected reports from our group, see: (f) Haldar, S.; Mahato,
S.; Jana, C. K. Asian J. Org. Chem. 2014, 3, 44. (g) Mahato, S.; Haque, M.
A.; Dwari, S.; Jana, C. K. RSC Adv. 2014, 4, 46214. (h) Haldar, S.; Roy, S.
K.; Maity, B.; Koley, D.; Jana, C. K. Chem. - Eur. J. 2015, 21, 15290.
6
g was utilized for Suzuki coupling with phenylboronic acid to
(i) Mandal, S.; Mahato, S.; Jana, C. K. Org. Lett. 2015, 17, 3762. For
obtain corresponding phenyl substituted imidazole 24 with an
excellent yield.
selected reports from others, see: (j) Zhang, C.; De, C. K.; Mal, R.;
Seidel, D. J. Am. Chem. Soc. 2008, 130, 416. (k) Richers, M. T.; Breugst,
M.; Platonova, A. Y.; Ullrich, A.; Dieckmann, A.; Houk, K. N.; Seidel, D.
J. Am. Chem. Soc. 2014, 136, 6123. (l) Manjappa, K. B.; Jhang, W.-F.;
Huang, S.-Y.; Yang, D.-Y. Org. Lett. 2014, 16, 5690. (m) Xie, Z.; Liu, L.;
Chen, W.; Zheng, H.; Xu, Q.; Yuan, H.; Lou, H. Angew. Chem., Int. Ed.
In summary, we have developed a novel annulation reaction of
a nitrosoarene and an aliphatic amine via an unprecedented
2
ortho-selective C(sp )−H amination of a nitrosoarene and
3
followed by α-C(sp )−H amination of aliphatic amines without
2
014, 53, 3904. (n) Pastine, S. J.; McQuaid, K. M.; Sames, D. J. Am.
Chem. Soc. 2005, 127, 12180. (o) Jurberg, I. D.; Peng, B.; Wostefeld, E.;
Wasserloos, M.; Maulide, N. Angew. Chem., Int. Ed. 2012, 51, 1950.
p) Mori, K.; Kurihara, K.; Yabe, S.; Yamanaka, M.; Akiyama, T. J. Am.
Chem. Soc. 2014, 136, 3744.
5) (a) van der Werf, A.; Selander, N. Org. Lett. 2015, 17, 6210.
aid of a metallic reagent/catalyst and an external oxidant. A wide
variety of bioactive ring-fused benzimidazoles were easily
prepared from readily available nitrosoarenes and N-heterocycles
in a mild and simple operation. Similarly, novel polycyclic
̈
(
imidazoles were prepared readily from the reaction of 2-hydroxy-
(
2
C-nitroso compounds. C(sp )−H amination via S ArH reaction
N
(b) Ingold, C. K. J. Chem. Soc., Trans. 1925, 127, 513. (c) Robertson, P.
W.; Hitchings, T. R.; Will, G. M. J. Chem. Soc. 1950, 808.
(6) (a) Sundberg, R. J.; Smith, R. H.; Bloor, J. E. J. Am. Chem. Soc. 1969,
91, 3392.
of o-halo-nitrosoarene was favored over conventional S Ar to
N
provide halogen (Cl, Br, I) containing products which are
otherwise difficult to prepare. DFT studies revealed the
involvement of H-bonding in controlling the ortho-selectivity
(7) (a) Penoni, A.; Volkmann, J.; Nicholas, K. M. Org. Lett. 2002, 4,
2
699. (b) Penoni, A.; Palmisano, G.; Zhao, Y.-L.; Houk, K. N.; Volkman,
J.; Nicholas, K. M. J. Am. Chem. Soc. 2009, 131, 653. (c) Murru, S.; Gallo,
A. A.; Srivastava, R. S. ACS Catal. 2011, 1, 29.
of C(sp )−H amination.
ASSOCIATED CONTENT
Supporting Information
■
(
8) Chakrabarty, S.; Chatterjee, I.; Tebben, L.; Studer, A. Angew.
Chem., Int. Ed. 2013, 52, 2968.
9) (a) Das, S.; Chakrabarty, S.; Daniliuc, C. G.; Studer, A. Org. Lett.
*
S
(
2
016, 18, 2784. (b) Das, S.; Daniliuc, C. G.; Studer, A. Org. Lett. 2016,
1
8, 5576.
Additional schemes, tables, and figures; experimental
details; copies of NMR spectra (PDF)
(
10) (a) Zuman, P.; Shah, B. Chem. Rev. 1994, 94, 1621. Direct C−H
amination was achieved using either bulky tert-butyl or adamentyl
amines. See (b) Lipilin, D. L.; Churakov, A. M.; Ioffe, S. L.; Strelenko, Y.
A.; Tartakovsky, V. A. Eur. J. Org. Chem. 1999, 1999, 29.
(
11) For review, see: (a) Mak
Heterocycl. Chem. 2013, 37, 51.
12) Patai, S. The Chemistry of functional groups, Supplement F2: The
̧ osza, M.; Wojciechowski, K. Top.
AUTHOR INFORMATION
■
*
(
chemistry of amino, nitroso, nitro and related group Part 1, 2; John Wiley &
Sons Ltd.: Munchen, Germany, 1996.
ORCID
(
13) (a) Makosza, M.; Winiarski, J. Acc. Chem. Res. 1987, 20, 282.
(b) Makosza, M.; Wojciechowski, K. Chem. Rev. 2004, 104, 2631.
c) Makosza, M. Chem. Soc. Rev. 2010, 39, 2855.
14) (a) Zhou, R.; Skibo, E. B. J. Med. Chem. 1996, 39, 4321. (b) Fahey,
Author Contributions
‡These authors contributed equally.
(
(
K.; O’Donovan, L.; Carr, M.; Carty, M. P.; Aldabbagh, F. Eur. J. Med.
Chem. 2010, 45, 1873. (c) Charlson, A. J.; Harington, J. S. Carbohydr.
Res. 1975, 43, 383.
Notes
The authors declare no competing financial interest.
(
15) (a) Nair, M. D.; Adams, R. J. Am. Chem. Soc. 1961, 83, 3518.
(
b) Suleman, A.; Skibo, E. B. J. Med. Chem. 2002, 45, 1211. (c) Baars, H.;
ACKNOWLEDGMENTS
We acknowledge financial support from SERB. H.K.S. is
recipient of Ramanujan fellowship (SB/S2/RJN-004/2015).
■
Beyer, A.; Kohlhepp, S. V.; Bolm, C. Org. Lett. 2014, 16, 536. (d) Xue,
D.; Long, Y.-Q. J. Org. Chem. 2014, 79, 4727. (e) Nguyen, T. B.;
Ermolenko, L.; Al-Mourabit, A. Green Chem. 2016, 18, 2966. (f) Nguyen,
T. B.; Ermolenko, L.; Al-Mourabit, A. Chem. Commun. 2016, 52, 4914.
(
16) A side reaction of reactive nitrosoarene and lower reactivity of
REFERENCES
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(
1
(
(
1
(
1614.
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1
(
(
2
D
Org. Lett. XXXX, XXX, XXX−XXX