ORGANIC
LETTERS
2011
Vol. 13, No. 6
1429–1431
Palladium-Catalyzed Denitrogenation
Reaction of 1,2,3-Benzotriazin-4(3H)-ones
Incorporating Isocyanides
Tomoya Miura, Yui Nishida, Masao Morimoto, Motoshi Yamauchi, and
Masahiro Murakami*
Department of Synthetic Chemistry and Biological Chemistry, Kyoto University,
Katsura, Kyoto 615-8510, Japan
Received December 27, 2010
ABSTRACT
1,2,3-Benzotriazin-4(3H)-ones and 1,2,3,4-benzothiatriazine 1,1(2H)-dioxide reacted with isocyanides in the presence of a palladium catalyst to
give 3-(imino)isoindolin-1-ones and 3-(imino)thiaisoindoline 1,1-dioxides, respectively, in high yield. An intermediate azapalladacycle was
generated through denitrogenation of the triazine moiety, and an isocyanide was incorporated therein.
Transition-metal-catalyzed annulation reactions trig-
gered by extrusion of gaseous small molecules have
emerged as a powerful strategy for efficient construction
of heterocyclic compounds. A heterometalacyclic inter-
mediate is generated as the key intermediate from an
organic platform and then incorporates an unsaturated
molecule to form a new heterocyclic framework. In
addition to rhodium(II)1 and palladium(0) complexes,2
nickel(0) complexes are also employed3,4 as the precatalyst
for such transformations. For example, phthalimide,3a
phthalic anhydride,3b and isatoic anhydride3c reacted with
alkynes in the presence of a nickel catalyst to give iso-
quinolin-1(2H)-ones, isochromen-1-ones, and quinolin-
4(1H)-ones, respectively, with concomitant extrusion of
CO or CO2. We have recently developed the nickel-cata-
lyzed annulation reactions of 1,2,3-benzotriazin-4(3H)-
ones with unsaturated compounds such as alkynes,5a
allenes,5b 1,3-dienes, and electron-deficient olefins.5c In
these reactions, the triazinone moiety is activated by
nickel(0), and with extrusion of N2, a five-membered
azanickelacycle is generated as the key intermediate.
(1) (a) Chuprakov, S.; Hwang, F. W.; Gevorgyan, V. Angew. Chem.,
Int. Ed. 2007, 46, 4757. (b) Horneff, T.; Chuprakov, S.; Chernyak, N.;
Gevorgyan, V.; Fokin, V. V. J. Am. Chem. Soc. 2008, 130, 14972. (c)
Chuprakov, S.; Kwok, S. W.; Zhang, L.; Lercher, L.; Fokin, V. V. J. Am.
Chem. Soc. 2009, 131, 18034. (d) Grimster, N.; Zhang, L.; Fokin, V. V.
J. Am. Chem. Soc. 2010, 132, 2510.
(2) (a) Shintani, R.; Murakami, M.; Hayashi, T. J. Am. Chem. Soc.
2007, 129, 12356. (b) Wang, C.; Tunge, J. A. J. Am. Chem. Soc. 2008,
130, 8118. (c) Nakamura, I.; Nemoto, T.; Shiraiwa, N.; Terada, M. Org.
Lett. 2009, 11, 1055. (d) Shintani, R.; Tsuji, T.; Park, S.; Hayashi, T.
J. Am. Chem. Soc. 2010, 132, 7508 and references cited therein.
(3) (a) Kajita, Y.; Matsubara, S.; Kurahashi, T. J. Am. Chem. Soc.
2008, 130, 6058. (b) Kajita, Y.; Kurahashi, T.; Matsubara, S. J. Am.
Chem. Soc. 2008, 130, 17226. (c) Yoshino, Y.; Kurahashi, T.; Matsubara,
S. J. Am. Chem. Soc. 2009, 131, 7494. (d) Miura, T.; Yamauchi, M.;
Murakami, M. Chem. Commun. 2009, 1470. (e) Ooguri, A.; Nakai,
K.; Kurahashi, T.; Matsubara, S. J. Am. Chem. Soc. 2009, 131, 13194.
(f) Miura, T.; Yamauchi, M.; Kosaka, A.; Murakami, M. Angew.
Chem., Int. Ed. 2010, 49, 4955. (g) Fujiwara, K.; Kurahashi, T.;
Matsubara, S. Org. Lett. 2010, 12, 4548.
(5) (a) Miura, T.; Yamauchi, M.; Murakami, M. Org. Lett. 2008, 10,
3085. (b) Yamauchi, M.; Morimoto, M.; Miura, T.; Murakami, M. J.
Am. Chem. Soc. 2010, 132, 54. (c) Miura, T.; Morimoto, M.; Yamauchi,
M.; Murakami, M. J. Org. Chem. 2010, 75, 5359.
(6) For examples of transition-metal-catalyzed cyclization reactions
incorporating isocyanides, see: (a) Zhang, M.; Buchwald, S. L. J. Org.
Chem. 1996, 61, 4498. (b) Kamijo, S.; Yamamoto, Y. J. Am. Chem. Soc.
2002, 124, 11940. (c) Shibata, T.; Yamashita, K.; Katayama, E.; Takagi,
K. Tetrahedron 2002, 58, 8661. (d) Onitsuka, K.; Suzuki, S.; Takahashi,
S. Tetrahedron Lett. 2002, 43, 6197. (e) Park, S.; Shintani, R.; Hayashi,
T. Chem. Lett. 2009, 38, 204. (f) Tobisu, M.; Imoto, S.; Ito, S.; Chatani,
N. J. Org. Chem. 2010, 75, 4835.
(7) For examples of the synthesis of 3-(imino)isoindolin-1-ones, see:
(a) Nan’ya, S.; Tange, T.; Maekawa, E. J. Heterocycl. Chem. 1985, 22,
449. (b) Takeuchi, H.; Eguchi, S. J. Chem. Soc., Perkin Trans. 1 1988,
2149. (c) Scherbakow, S.; Namyslo, J. C.; Gjikaj, M.; Schmidt, A.
Synlett 2009, 1964. (d) Wang, J.; He, Z.; Chen, X.; Song, W.; Lu, P.;
Wang, Y. Tetrahedron 2010, 66, 1208.
(4) For related reaction evolving CO, see: O’Brien, E. M.; Bercot,
E. A.; Rovis, T. J. Am. Chem. Soc. 2003, 125, 10498.
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10.1021/ol103143a
2011 American Chemical Society
Published on Web 02/14/2011