ORGANIC
LETTERS
1999
Vol. 1, No. 11
1725-1727
New Synthetic Method of Diorganyl
Selenides: Palladium-Catalyzed Reaction
of PhSeSnBu3 with Aryl and Alkyl
Halides
Yutaka Nishiyama,* Keiji Tokunaga, and Noboru Sonoda*
Department of Applied Chemistry, Faculty of Engineering & High Technology
Research Center, Kansai UniVersity, Suita, Osaka 564-8680, Japan
Received August 16, 1999
ABSTRACT
Palladium complexes such as Pd(PPh3)4 catalyzed the reaction of phenyl tributylstannyl selenide (PhSeSnBu3) with aryl and alkyl halides,
giving the corresponding diaryl and alkylaryl selenides in moderate to good yields.
In the organic chemistry of selenium, the key intermediates
are often diorganyl selenides, and much effort is being
devoted to accomplishing the synthesis of these compounds.1
However, many synthetic methods sometimes suffer from
the improper handling of selenium reagents used as selenium
sources, because of their instability against air and/or
moisture. Therefore, the development of new synthetic
methods using stable selenium reagents would have signifi-
cant synthetic value.
and alkyl halides in the presence of a catalytic amount of
Pd(PPh3)4 took place efficiently, giving the corresponding
(2) There are some reports on the palladium complex-catalyzed reaction
of aryl and alkyl halides with organic heteroatom compounds having
heteroatom-heteroatom bonds. (i) B-B: Ishiyama, T.; Murata, M.;
Miyaura, N. J. Org. Chem. 1995, 60, 7508. (ii) Si-Si: Matsumoto, H.;
Nagashima, S.; Yoshihiro, K.; Nagai, Y. J. Organomet. Chem. 1975, 85,
C1. Matsumoto, H.; Yoshihiro, K.; Nagashima, S.; Watanabe, H.; Nagai,
Y. J. Organomet. Chem. 1977, 128, 401. Matsumoto, H.; Nagashima, S.;
Kato, T.; Nagai, Y. Angew. Chem. 1978, 90, 288. Faboru, C.; Griffiths, R.
W.; Pidcock, A. J. Organomet. Chem. 1982, 225, 331. Nakano, T.;
Takahashi, M.; Ashizawa, T.; Arai, T.; Seki, S.; Matsumoto, H.; Nagai, Y.
Chem. Lett. 1982, 613. Hiyama, T.; Obayashi, M.; Mori, I.; Nozaki, H. J.
Org. Chem. 1983, 48, 912. Hatanaka, Y. Hiyama, T. Tetrahdron Lett. 1987,
28, 4715. (iii) Al-Si: Trost, B. M.; Yoshida, J. Tetrahedron Lett. 1983,
24, 4895. (iv) Si-P: Tunney, S. E.; Stille, J. K. J. Org. Chem. 1987, 52,
748. (v) Si-Sn: Mori, M.; Kaneta, N.; Shibasaki, M. J. Org. Chem. 1991,
56, 3486. (vi) S-Sn: Beletzkaya, I. P. J. Organomet. Chem. 1983, 250,
551. Carpita, A.; Rossi, R.; Scamuzzi, B. Tetrahedron Lett. 1989, 30, 2699.
Juxiang, C.; Crisp, G. T. Synth. Commun. 1992, 22, 683. (vii) Sn-Sn:
Farina, V.; Hauck, S. I. J. Org. Chem. 1991, 56, 4317. Kosugi, M.; Shimizu,
K.; Ohtani, A.; Migita, T. Chem. Lett. 1981, 829.
Transition metal complex-catalyzed reactions of aryl
halides with organoheteroatom compounds having M-M′
(M and M′ ) heteroatom) bonds are now widely used for
the synthesis of various heteroatom-containing com-
pounds;2 however, similar reactions of aryl halides with
organoselenium compounds containing a selenium-hetero-
atom bond have not been found. In the course of our study
on the utilization of phenyl tributylstannyl selenide (Ph-
SeSnBu3) (1),3,4 which is stable against air and moisture, in
organic reactions, we found that the reaction of 1 with aryl
(3) Nishiyama, Y.; Aoyama, S.; Hamanaka, S. Phosphorus, Silicon, Sulfur
1993, 65, 1245. Nishiyama, Y.; Ohashi, H.; Itoh, K.; Sonoda, N. Chem.
Lett. 1998, 159.
(4) The other applications of organoselenium compounds having a Se-
Sn bond are very few due to the lack of methods for the activation of the
selenium-tin bond.5 See: Shimada, K.; Okuse, S.; Takikawa, Y. Bull.
Chem. Soc. Jpn. 1992, 65, 2848. Segi, M.; Kato, M.; Nakajima, T.; Suga,
S. Tetrahedron Lett. 1991, 32, 7427. Segi, M.; Kojima, T.; Nakajima, T.;
Suga, S. Synlett 1991, 105. Harpp, D. N.; Gingras, M. J. Am. Chem. Soc.
1988, 110, 7737. Steliou, K.; Mrani, M. J. Am. Chem. Soc. 1982, 104, 3104.
Baudler, M.; Suchomel, H.; Fu¨rstenberg, G.; Schings, U. Angew. Chem.,
Int. Ed. Engl. 1981, 20, 1044. Crosse, B. C.; Hutson, G. V. J. Chem. Soc.
A 1967, 2014.
(1) Krief, A.; Hevesi, L. In Organoselenium Chemistry, Vol. 1; Springer-
Verlag: Berlin, 1988. Paulmier, C. In Selenium Reagents and Intermediates
in Organic Synthesis; Pergamon Press: Oxford, 1986. Patai, S.; Rappoport,
Z. In The Chemistry of Organic Selenium and Tellurium Compounds, Vols.
1 and 2; 1986. Krief, A. In ComprehensiVe Organic Synthesis, Vol. 3; Trost,
B. M., Eds.; Pergamon Press: Oxford, 1991; pp 85-192 and references
therein.
10.1021/ol990233z CCC: $18.00 © 1999 American Chemical Society
Published on Web 10/28/1999