ORGANIC
LETTERS
2
001
Vol. 3, No. 25
103-4105
Palladium-Catalyzed Cross-Coupling
Reaction of Triarylbismuths with Aryl
Halides and Triflates
4
†
†
,†
‡
Maddali L. N. Rao, Osamu Yamazaki, Shigeru Shimada,* Toshifumi Tanaka,
‡
,†,‡,§
Yohichi Suzuki, and Masato Tanaka*
National Institute of AdVanced Industrial Science and Technology (AIST),
Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan,
and Department of Industrial Chemistry, College of Industrial Technology,
Nihon UniVersity, 1-2-1, Izumi-cho, Narashino, Chiba 275-8575, Japan
Received October 10, 2001
ABSTRACT
Palladium-catalyzed cross-coupling reaction of triarylbismuths with aryl bromides, iodides, and triflates proceeded efficiently in the presence
of K CO or CsF.
2
3
Transition metal-catalyzed cross-coupling reaction of orga-
nometallic compounds with organic halides and triflates is
one of the most important reactions for making C-C bonds.
recently demonstrated that organobismuth compounds are
actually useful reagents for the palladium-catalyzed cross-
coupling reaction with aryl and vinyl triflates by using
1
4
,5
Although various organometallic compounds such as orga-
notin, -boron, -silicon, -zinc, and -magnesium compounds
have been successfully utilized for the cross-coupling reac-
tions, organobismuth compounds have not been well stud-
organobismuth dialkoxides 1. Triarylbismuths are more
2
,3
ied. Since bismuth is known to be a low-level toxic
element, organobismuth compounds are potentially useful
candidates for environmentally benign reagents. We have
†
National Institute of Advanced Industrial Science and Technology.
Nihon University.
E-mail: m.tanaka@aist.go.jp.
‡
favorable reagents than 1 because they are easier to prepare
than the dialkoxides (some triarylbismuths are commercially
available), are stable to moisture, and can be handled and
stored under air, while 1 are sensitive to moisture. However,
triarylbismuths were found to be much less reactive than 1
§
(
1) Metal-Catalyzed, Cross-Coupling Reactions; Diederich, F., Stang, P.
J., Eds.; Wiley-VCH: Weinheim, 1998.
2) Suzuki, H.; Ikegami, T.; Matano, Y. Synthesis 1997, 249. Suzuki,
(
H.; Matano, Y. In Chemistry of Arsenic, Antimony and Bismuth; Norman,
N. C., Ed.; Blackie Academic & Professional: London, 1998; Chapter 6.
Elliott, G. I.; Konopelski, J. P. Tetrahedron 2001, 57, 5683.
4
for the cross-coupling reaction with organic triflates. Here
we have examined the effect of additives on the reactivity
(3) 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. Wada, M.;
Ohki, H. J. Synth. Org. Chem. Jpn. 1989, 47, 425. 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. Huang,
X.; Wu, J. L. Chin. Chem. Lett. 1997, 8, 759. Ohe, T.; Tanaka, T.; Kuroda,
M.; Cho, C. S.; Ohe, K.; Uemura, S. Bull. Chem. Soc. Jpn. 1999, 72, 1851.
Kang, S. K.; Ryu, H. C.; Kim, J. W. Synth. Commun. 2001, 31, 1021. Kang,
S. K.; Ryu, H. C.; Lee, S. W. Synth. Commun. 2001, 31, 1027. Kang, S.
K.; Ryu, H. C.; Hong, Y. T.; Kim, M. S.; Lee, S. W.; Jung, J. H. Synth.
Commun. 2001, 31, 2365.
(4) Rao, M. L. N.; Shimada, S.; Tanaka, M. Org. Lett. 1999, 1, 1271.
(5) Shimada, S.; Rao, M. L. N.; Tanaka, M. Organometallics 2000, 19,
931.
1
0.1021/ol016885g CCC: $20.00 © 2001 American Chemical Society
Published on Web 11/15/2001