LETTER
Catalysts for the Ullmann and Sonogashira Reactions
1295
General Procedure for Perovskite-Catalyzed Sonogashira Re-
action
(8) Ullmann, F. Chem. Ber. 1903, 2389.
(9) Ley, S. V.; Thomas, A. W. Angew. Chem. Int. Ed. 2003, 42,
5400.
(10) Nelson, T. D.; Crouch, R. D. Org. React. 2004, 63, 265.
(11) Marcoux, J. F.; Doye, S.; Buchwald, S. L. J. Am. Chem. Soc.
1997, 119, 10539.
(12) Kwong, F. Y.; Buchwald, S. L. Org. Lett. 2002, 4, 3517.
(13) Capdevielle, P.; Maumy, M. Tetrahedron Lett. 1993, 34,
1007.
The appropriate perovskite (0.008 mmol, 2.5 mol%) was added to a
mixture of aryl halide (0.315 mmol, 1.0 equiv), alkyne (0.346
mmol, 1.1 equiv), Et3N (1.26 mmol, 4.0 equiv) and 5% H2O in DMF
or DMA (1.1 mL). The reaction tube was flushed with argon, fitted
with a reflux condenser and heated at 120 °C for 6–24 h. The reac-
tion mixture was diluted with Et2O (2 mL) and poured into 10% aq
LiCl (15 mL). The aqueous phase was separated and extracted with
Et2O (3 × 10 mL). Combined organic phases were concentrated in
vacuo and purified by silica gel chromatography to afford the cou-
pled product.
(14) Ma, D. W.; Xia, C. F. Org. Lett. 2001, 3, 2583.
(15) Ma, D. W.; Zhang, Y. D.; Yao, J. C.; Wu, S. H.; Tao, F. G.
J. Am. Chem. Soc. 1998, 120, 12459.
(16) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett.
1975, 4467.
(17) Cassar, L. J. Organomet. Chem. 1975, 93, 253.
(18) Dieck, H. A.; Heck, F. R. J. Organomet. Chem. 1975, 93,
259.
(19) Soheili, A.; Albaneze-Walker, J.; Murry, J. A.; Dormer, P.
G.; Hughes, D. L. Org. Lett. 2003, 5, 4191.
(20) Chouzier, S.; Gruber, M.; Djakovitch, L. J. Mol. Catal. A:
Chem. 2004, 212, 43.
(21) Saphier, M.; Masarwa, A.; Cohen, H.; Meyerstein, D. Eur. J.
Inorg. Chem. 2002, 1226.
Acknowledgment
The authors would like to thank Daihatsu Motor Co. Ltd. and Hok-
ko Chemical Industry Co. Ltd. for their kind gift of perovskites, the
Novartis Research Fellowship (to SVL), The Royal Society for a
URF (to MDS), GlaxoSmithKline and Insight Faraday for a CASE
award (to SPA) and the French Foreign Office for a Lavoisier fel-
lowship (to SL).
(22) Park, S. B.; Alper, H. Chem. Commun. 2004, 1306.
(23) Novak, Z.; Szabo, A.; Repasi, J.; Kotschy, A. J. Org. Chem.
2003, 68, 3327.
(24) Wang, L.; Li, P. H.; Zhang, Y. C. Chem. Commun. 2004,
514.
(25) Son, S. U.; Jang, Y.; Park, J.; Na, H. B.; Park, H. M.; Yun,
H. J.; Lee, J.; Hyeon, T. J. Am. Chem. Soc. 2004, 126, 5026.
(26) Leadbeater, N. E.; Marco, M.; Tominack, B. J. Org. Lett.
2003, 5, 3919.
(27) Thathagar, M. B.; Beckers, J.; Rothenberg, G. Green Chem.
2004, 6, 215.
References
(1) Attfield, J. P. Int. J. Inorg. Mater. 2001, 3, 1147.
(2) Cava, R. J. J. Am. Ceram. Soc. 2000, 83, 5.
(3) Ramirez, A. P. J. Phys.: Condens. Mat. 1997, 9, 8171.
(4) Nishihata, Y.; Mizuki, J.; Akao, T.; Tanaka, H.; Uenishi, M.;
Kimura, M.; Okamoto, T.; Hamada, N. Nature 2002, 418,
164.
(5) Smith, M. D.; Stepan, A. F.; Ramarao, C.; Brennan, P. E.;
Ley, S. V. Chem. Commun. 2003, 2652.
(6) Andrews, S. P.; Stepan, A. F.; Ley, S. V.; Tanaka, H.; Smith,
M. D. Adv. Synth. Catal. 2005, in press.
(28) Appukkuttan, P.; Dehaen, W.; Van der Eycken, E. Eur. J.
Org. Chem. 2003, 4713.
(7) Raveau, B.; Rao, C. N. R. Transition Metal Oxides:
Structure, Properties and Synthesis of Ceramic Oxides; John
Wiley & Sons: Oxford, 1998.
Synlett 2005, No. 8, 1291–1295 © Thieme Stuttgart · New York