ORGANIC
LETTERS
2004
Vol. 6, No. 20
3597-3599
A New Ketone Synthesis by
Palladium-Catalyzed Cross-Coupling
Reactions of Esters with Organoboron
Compounds
Hiroto Tatamidani, Fumitoshi Kakiuchi, and Naoto Chatani*
Department of Applied Chemistry, Faculty of Engineering, Osaka UniVersity,
Suita, Osaka 565-0871, Japan
Received July 29, 2004
ABSTRACT
The palladium-catalyzed coupling reaction of 2-pyridyl esters with organoboron compounds is described. The reaction is compatible with
various functional groups and proceeds under mild reaction conditions. The coordination of the nitrogen atom to Pd is a key step for efficient
reaction.
Recently, palladium-catalyzed cross-coupling reactions have
become one of the most powerful and reliable methods for
C-C bond formation and a variety of coupling reactions have
been developed.1 It is no exaggeration to say that complicated
molecules cannot be constructed without the use of coupling
reactions. Among coupling reactions, the Suzuki-Miyaura
reaction is widely used in the laboratory or industrial scale
because of its reliability, high functional group compatibility,
the nontoxicity of organoboron compounds, easy handling,
and mild reaction conditions.2 The carbonylative Miyaura-
Suzuki reaction was also accomplished in the presence of
carbon monoxide to give ketones.3 The use of carboxylic
acid derivatives as the substrates represents an attractive
alternative route to ketones instead of the carbonylative
coupling reaction of halides. In fact, acid chlorides have
already been applied to the Suzuki-Miyaura reaction.4 In
recent years, the progress of palladium-catalyzed coupling
reactions of carboxylic acid derivatives has been remarkable,
and various carboxylic acid derivatives have been used by
several groups.5 The reaction of acid anhydrides was reported
by Goossen6 and Yamamoto7 independently, and they
showed that carboxylic acids could be directly used as
starting material by being converted to acid anhydrides in
situ. It was found that thioesters are also suitable substrates
for coupling reactions, as reported by Terfort8 and Liebe-
skind.9 Yamamoto also reported a coupling reaction of esters
with organoboron compounds.10 However, the reaction was
limited to electronically activated esters, such as perfluoro-
aliphatic carboxylic esters. Recently, we demonstrated that
even esters which are not activated by electron-withdrawing
(4) (a) Cho, C. S.; Itotani, K.; Uemura, S. J. Organomet. Chem. 1993,
443, 253. (b) Bumagin, N. A.; Bykov, V. V. Tetrahedron 1997, 53, 14437.
(c) Bumagin, N. A.; Korolev, D. N. Tetrahedron Lett. 1999, 40, 3057. (d)
Haddach, M.; McCarthy, J. R. Tetrahedron Lett. 1999, 40, 3109. (e)
Kabalka, G. W.; Malladi, R. R.; Tejedor, D.; Kelley, S. Tetrahedron Lett.
2000, 41, 999. (f) Chen, H.; Deng, M.-Z. Org. Lett. 2000, 2, 1649. (g)
Wang, J.-X.; Wei, B.; Hu, Y.; Liu, Z.; Yang, Y. Synth. Commun. 2001, 31,
3885. (h) Urawa, Y.; Ogura, K. Tetrahedron Lett. 2003, 44, 271. (i)
Urakawa, Y.; Nishiura, K.; Souda, S.; Ogura, K. Synthesis 2003, 2882.
(5) Zapf, A. Angew. Chem., Int. Ed. 2003, 42, 5394.
(6) Goossen, L. J.; Ghosh, K. Eur. J. Org. Chem. 2002, 3254 and
references therein.
(7) Kakino, R.; Narahashi, H.; Shimizu, I.; Yamamoto, A. Bull. Chem.
Soc. Jpn. 2002, 75, 1333 and references therein..
(1) For recent reviews on cross-coupling, see: Tsuji, J. Palladium
Reagents and Catalysts; Wiley: Chichester, U.K., 1995; pp 290-422.
Metal-catalyzed Cross-coupling Reactions; Diedrich, F., Stang, P. J., Eds.;
Wiley-VCH: Weinheim, 1998. Hassan, J.; Sevignon, M.; Gozzi, C.; Schulz,
E.; Lemaire, M. Chem. ReV. 2002, 102, 1359.
(2) For recent reviews on the Suzuki-Miyaura coupling, see: Miyaura,
N.; Suzuki, A. Chem. ReV. 1995, 95, 2457. Miyaura, N. J. Organomet.
Chem. 2002, 653, 54. Suzuki, A. J. Organomet. Chem. 2002, 653, 83. Kotha,
S.; Lahiri, K.; Kashinath, D. Tetrahedron 2002, 58, 9633. Miyaura, N. Top.
Curr. Chem. 2002, 219, 11.
(8) Zeysing, B.; Gosch, C.; Terfort, A. Org. Lett. 2000, 2, 1843.
(9) (a) Savarin, C.; Srogl, J.; Liebeskind, L. S. Org. Lett. 2000, 2, 3229.
(b) Liebeskind, L. S.; Srogl, J. J. Am. Chem. Soc. 2000, 122, 11260. (c)
Yu, Y.; Liebeskind, L. S. J. Org. Chem. 2004, 69, 3554.
(3) Ishiyama, T.; Miyaura, N.; Suzuki, A. Bull. Chem. Soc. Jpn. 1991,
64, 1999.
10.1021/ol048513o CCC: $27.50
© 2004 American Chemical Society
Published on Web 09/10/2004