pubs.acs.org/joc
they are often used for designing many pharmacological
Synthesis of 2,4-Diiodoquinolines via the
Photochemical Cyclization of o-Alkynylaryl
Isocyanides with Iodine
molecules.1 In particular, quinoline derivatives containing
halogen atoms are one of the significant raw materials for
preparing functionalized quinolines because of their
bioactivities2 and synthetic utilities, which result from the
fact that selective conversion of C-X bonds (X = halogen
atoms) into C-C or C-E bonds (E = O, N, S) is possible
through the use of organic lithium reagents, Grignard re-
agents, or transition metal catalysts.3 Although many meth-
ods have been developed for the synthesis of quinoline
frameworks, highly selective methods for the preparation
of quinoline derivatives under mild reaction conditions
would be useful in advanced research areas.4,5
Takenori Mitamura and Akiya Ogawa*
Department of Applied Chemistry, Graduate School of
Engineering, Osaka Prefecture University, 1-1 Gakuen-cho,
Nakaku, Sakai, Osaka 599-8531, Japan
Received November 1, 2010
Isocyanides are one of the promising precursors for the
preparation of N-heterocycles such as pyrroles, indoles, and
quinolines in the presence of nucleophiles, transition metal
catalysts, and radical mediators.6-8 In contrast to the many
reports on the synthesis of pyrrole and indole derivatives,
selective preparation methods for quinoline derivatives are
limitated.9 Recently, we have developed a method for the
photochemical cyclization of o-alkynylaryl isocyanides with
diphenyl ditelluride; the method affords the corresponding
2,4-bistellurated quinolines.10 In this paper, we report the
Upon photoirradiation of o-alkynylaryl isocyanides in
the presence of iodine, the intramolecular cyclization of
o-alkynylaryl isocyanides proceeds to afford the corre-
sponding 2,4-diiodoquinolines in good yields. 2,4-Diio-
doquinolines can be employed in transition metal-
catalyzed cross-coupling reactions.
(4) For recent reports on the synthesis of quinolines, see the following
references: (a) Cho, C. S.; Oh, B. H.; Kim, J. S.; Kim, T.-J.; Shim, S. C.
ꢀ
Chem. Commun. 2000, 1885. (b) Pouysegu, L.; Avellan, A.-V.; Quideau, S. J.
Org. Chem. 2002, 67, 3425. (c) Mehta, B. K.; Yanagisawa, K.; Shiro, M.;
Kotsuki, H. Org. Lett. 2003, 5, 1605. (d) McNaughton, B. R.; Miller, B. L.
Org. Lett. 2003, 5, 4257. (e) Dormer, P. G.; Eng, K. K.; Farr, R. N.;
Humphrey, G. R.; McWilliams, J. C.; Reider, P. J.; Sager, J. W.; Volante,
R. P. J. Org. Chem. 2003, 68, 467. (f) Palimkar, S. S.; Siddiqui, S. A.; Daniel,
T.; Lahoti, R. J.; Srinivasan, K. V. J. Org. Chem. 2003, 68, 9371. (g) Shindoh,
N.; Tokuyama, H.; Takemoto, Y.; Takasu, K. J. Org. Chem. 2008, 73, 7451.
(5) For the synthesis of quinolines containing halogen atoms, see the
following references: (a) Takaya, J.; Kagoshima, H.; Akiyama, T. Org. Lett.
Quinolines are contained in numerous natural products
such as alkaloids and bioactive compounds, and therefore,
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DOI: 10.1021/jo1021772
r
Published on Web 01/18/2011
J. Org. Chem. 2011, 76, 1163–1166 1163
2011 American Chemical Society