ORGANIC
LETTERS
2003
Vol. 5, No. 26
4963-4966
Tetraorganoindates as Nucleophilic
Coupling Partners in Pd-Catalyzed
Cross-Coupling Reactions
Phil Ho Lee,* Sung Wook Lee, and Dong Seomoon
Department of Chemistry, Kangwon National UniVersity,
Chunchon 200-701, Republic of Korea
Received September 26, 2003
ABSTRACT
In situ-generated tetraorganoindate complexes from the reaction of 1 equiv of indium trichloride with 4 equiv of appropriate organometallics
are efficient nucleophiles in Pd-catalyzed cross-coupling reactions. In this novel reaction tetraorganoindates containing methyl, 1°- and 2°-
alkyl, vinyl, alkynyl, and aryl groups transfer the four organic groups to a variety of electrophiles with high atom efficiency.
Synthetic applications of metallic indium have attracted much
attention during the past decade due to this metal’s chemical
properties in terms of reactivity, selectivity, and low toxicity.1
Among many indium-mediated reactions, the Barbier-type
allylation reaction using allylic indium sesquihalides is most
widely applied in organic synthesis.2 Recently, we reported
Pd-catalyzed cross-coupling reactions of in situ-generated
allylindium3 or allenylindium4 reagents and carbonylative
cross-coupling reactions of in situ-generated triorganoindium5
with a variety of electrophiles. Also, it was found that a var-
iety of organoindium reagents could be used in Pd-catalyzed
cross-coupling reactions as nucleophilic coupling partners.6
During the course of this study,7 we considered the possibility
of extending the metal-catalyzed crosscoupling reaction by
using indate complexes. While tetramethylindate was pre-
(5) (a) Lee, P. H.; Lee, S. W.; Lee, K. Org. Lett. 2003, 5, 1103. (b)
Pena, M. A.; Sestelo, J. P.; Sarandeses, L. A. Synthesis 2003, 780.
(6) (a) Nomura, R.; Miyazaki, S.-I.; Matsuda, H. J. Am. Chem. Soc. 1992,
114, 2738. (b) Perez, I.; Sestelo, J. P.; Sarandeses, L. A. Org. Lett. 1999,
1, 1267. (c) Gelman, D.; Schumann, H.; Blum, J. Tetrahedron Lett. 2000,
41, 7555. (d) Perez, I.; Sestelo, J. P.; Sarandeses, L. A. J. Am. Chem. Soc.
2001, 123, 4155. (e) Hirashita, T.; Yamamura, H.; Kawai, M.; Araki, S.
Chem. Commun. 2001, 387. (f) Takami, K.; Yorimitsu, H.; Shnokubo, H.;
Matsubara, S.; Oshima, K. Org. Lett. 2001, 3, 1997. (g) Pena, M. A.; Perez,
I.; Sestelo, J. P.; Sarandeses, L. A. Chem. Commun. 2002, 2246.
(7) (a) Lee, P. H.; Bang, K.; Lee, K.; Lee, C.-H.; Chang, S. Tetrahedron
Lett. 2000, 41, 7521. (b) Lee, P. H.; Lee, K.; Sung, S.-Y.; Chang, S. J.
Org. Chem. 2001, 66, 8646. (c) Lee, P. H.; Lee, K.; Kim, S. Org. Lett.
2001, 3, 3205. (d) Lee, P. H.; Ahn, H.; Lee, K.; Sung, S.-Y.; Kim, S.
Tetrahedron Lett. 2001, 42, 37. (e) Lee, P. H.; Sung, S.-Y.; Lee, K.; Chang,
S. Synlett 2002, 146. (f) Iwasawa, N.; Miura, T.; Kiyota, K.; Kusami, H.;
Lee, K.; Lee, P. H. Org. Lett. 2002, 4, 4463. (g) Miura, T.; Kiyota, K.;
Kusama, H.; Lee, K.; Kim, H.; Kim, S.; Lee, P. H.; Iwasawa, N. Org. Lett.
2003, 5, 1725. (h) Lee, P. H.; Seomoon, D.; Lee, K.; Heo, Y. J. Org. Chem.
2003, 68, 2510. (i) Lee, K.; Kim, H.; Miura, T.; Kiyota, K.; Kusama, H.;
Kim, S.; Iwasawa, N.; Lee, P. H. J. Am. Chem. Soc. 2003, 125, 9682. (j)
Lee, P. H.; Seomoon, D.; Kim, S. D.; Nagaiah, K.; Damle, S. V.; Lee, K.
Synthesis 2003, 2189.
(1) (a) Li, C.-J. Chem. ReV. 1993, 93, 2023. (b) Cintas, P. Synlett 1995,
1087. (c) Li, C.-J. Tetrahedron 1996, 52, 5643. (d) Li, C.-J.; Chan, T.-H.
Organic Reactions in Aqueous Media; Wiley: New York, 1997. (e) Li,
C.-J.; Chan, T.-H. Tetrahedron 1999, 55, 11149. (f) Babu, G.; Perumal, P.
T. Aldrichimica Acta 2000, 33, 16. (g) Chauhan, K. K.; Frost, C. G. J.
Chem. Soc., Perkin Trans. 1 2000, 3015. (h) Pae, A. N.; Cho, Y. S. Curr.
Org. Chem. 2002, 6, 715. (i) Podlech, J.; Maier, T. C. Synthesis 2003, 633.
(2) (a) Araki, S.; Ito, H.; Butsugan, Y. J. Org. Chem. 1988, 53, 1831.
(b) Li, C.-J.; Chan, T. H. Tetrahedron Lett. 1991, 32, 7017. (c) Lee, P. H.;
Seomoon, D.; Lee, K. Bull. Korean Chem. Soc. 2001, 22, 1380. (d) Bang,
K.; Lee, K.; Park, Y. K.; Lee, P. H. Bull. Korean Chem. Soc. 2002, 23,
1272.
(3) (a) Lee, P. H.; Sung, S.-Y.; Lee, K. Org. Lett. 2001, 3, 3201. (b)
Lee, K.; Lee, J.; Lee, P. H. J. Org. Chem. 2002, 67, 8265.
(4) Lee, K.; Seomoon, D.; Lee, P. H. Angew. Chem., Int. Ed. 2002, 41,
3901.
10.1021/ol035883o CCC: $25.00 © 2003 American Chemical Society
Published on Web 11/27/2003