ORGANIC
LETTERS
1999
Vol. 1, No. 8
1271-1273
Palladium Complex-Catalyzed
Cross-Coupling Reaction of
Organobismuth Dialkoxides with
Triflates
Maddali L. N. Rao, Shigeru Shimada, and Masato Tanaka*
National Institute of Materials and Chemical Research,
Tsukuba, Ibaraki 305-8565, Japan
Received August 13, 1999
ABSTRACT
Pd(PPh3)4 catalyzes cross-coupling reaction between organobismuth alkoxides and aryl and vinyl triflates.
Use of heteroatom compounds in organic synthesis is a
rapidly growing area of research. Our successful development
of transition metal-catalyzed reactions of heteroatom com-
pounds1 has led us to scrutinize organobismuth compounds,
since bismuth is one of the least used elements in organic
synthesis. Although the unique performance of bismuth salts
as Lewis acid catalysts or reagents is becoming evident,2
the application of organobismuth reagents in organic syn-
thesis is still very limited.3,4 Organobismuth compounds are
normally nontoxic and potentially meet the recent require-
ment for the reagent, process, and product of little or no risk
to humans and environment, which is a major contemporary
concern in the chemistry community.5 It is in this respect
that we became interested in the opportunity for use of
bismuth reagents in organic synthesis. Recently we prepared
new organobismuth dialkoxides, 1a-1d.6 We report herein
(1) For selected examples, see: Han, L.-B.; Tanaka; M. J. Am. Chem.
Soc. 1996, 118, 1571. Han, L.-B.; Choi, N.; Tanaka; M. Organometallics
1996, 15, 3259. Han, L.-B.; Choi, N.; Tanaka; M. J. Am. Chem. Soc. 1996,
118, 7000. Onozawa, S.-y.; Hatanaka, Y.; Choi, N.; Tanaka; M. Organo-
metallics 1997, 16, 5389. Onozawa, S.-y.; Hatanaka, Y.; Tanaka; M. Chem.
Commun. 1997, 1229. Han, L.-B.; Hua, R.; Tanaka; M. Angew. Chem. Int.
Ed. 1998, 37, 94. Han, L.-B.; Tanaka; M. J. Am. Chem. Soc. 1998, 120,
8249.
(2) Recent examples: Komatsu, N.; Uda, M.; Suzuki, H. Chem. Lett.
1997, 1229. Wada, M.; Takahashi, T.; Domae, T.; Fukuma, T.; Miyoshi,
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E.; Postel, M. New J. Chem. 1997, 21, 495. Le Boisselier, V.; Postel, M.;
Dun˜ach, E. Chem. Commun. 1997, 95. Robert, H.; Garrigues, B.; Dubac,
J. Tetrahedron Lett. 1998, 39, 1161. Repichet, S.; Le Roux, C.; Dubac, J.;
Desmurs, J. R. Eur. J. Org. Chem. 1998, 2743. Winum, J. Y.; Kamal, M.;
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1998, 28, 1737.
(3) Recent review: Suzuki, H.; Ikegami, T.; Matano, Y. Synthesis 1997,
249.
(4) Examples of Pd complex-mediated or -catalyzed reaction of orga-
nobismuth compounds: Asano, R.; Moritani, I.; Fujiwara, Y.; Teranishi,
S. Bull. Chem. Soc. Jpn. 1973, 46, 2910. Kawamura, T.; Kikukawa, K.;
Takagi, M.; Matsuda, T. Bull. Chem. Soc. Jpn. 1977, 50, 2021. Barton, D.
H. R.; Ozbalik, N.; Ramesh, M. Tetrahedron 1988, 44, 5661. Suzuki, H.;
Murafuji, T.; Azuma, N. J. Chem. Soc., Perkin Trans. 1 1992, 1593. Cho,
C. S.; Yoshimori, Y.; Uemura, S. Bull. Chem. Soc. Jpn. 1995, 68, 950.
(5) Green Chemistry; ACS Symposium Series 626; Anastas, P. T.,
Williamson, T. C., Eds.; American Chemical Society: Washington, DC,
1996.
10.1021/ol990941k CCC: $18.00 © 1999 American Chemical Society
Published on Web 09/23/1999