1606
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34, 1625; (g) Cai, M.-Z.; Song, C.-S.; Huang, X. Synth.
Commun. 1997, 27, 1935; (h) Crisp, G. T.; Turner, P. D.;
Stephens, K. A. J. Organomet. Chem. 1998, 570, 219; (i)
Mori, A.; Kawashima, J.; Shimada, T.; Suguro, M.;
Hirabayashi, K.; Nishihara, Y. Org. Lett. 2000, 2, 2935; (j)
Fukuyama, T.; Shinmen, M.; Nishitani, S.; Sato, M.; Ryu,
I. Org. Lett. 2002, 4, 1691; (k) Reosch, K.; Larock, R. C.
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251.
20 h) and the formation of the cyclisation product was
observed. Using similar conditions in absence of palla-
dium catalyst, but in the presence of potassium car-
bonate, no formation of cyclisation product was
detected. Larger amounts of these cyclisation products
were observed in the presence of electron-poor aryl
bromides (Table 1, entries 5 and 6; Table 2, entries 26,
28–31, 35 and 37). Catalysed reactions performed with
4-bromoanisole and pent-1-yn-5-ol or with isolated 1-(4-
methoxyphenyl)pent-1-yn-5-ol, did not lead to the for-
mation of cyclisation products.
3. For examples of reactions using aryl halides and but-1-yn-
4-ol: (a) Muehldorf, A. V.; Guzman-Perez, A.; Kluge, A.
F. Tetrahedron Lett. 1994, 35, 8755; (b) Mori, A.;
Shimada, T.; Kondo, T.; Sekiguchi, A. Synlett 2001,
649; (c) Pal, M.; Parasuraman, K.; Gupta, S.; Rao, K.;
Yeleswarapu, R. Synlett 2002, 1976, and Refs. 2c–e,k.
4. For examples of reactions using aryl halides and pent-1-
yn-5-ol: Brimble, M.; Pavia, G. S.; Stevenson, R. J.
Tetrahedron Lett. 2002, 43, 1735, and Ref. 2c.
5. For examples of reactions using aryl halides and hex-1-yn-
6-ol: Nguefack, J.-F.; Bolitt, V.; Sinou, D. Tetrahedron
Lett. 1996, 37, 5527.
6. (a) Herrmann, W. A.; Reisinger, C.-P.; Spiegler, M. J.
Organomet. Chem. 1998, 557, 93; (b) Nakamura, K.;
Okubo, H.; Yamaguchi, M. Synlett 1999, 549; (c)
McGuinness, D.; Cavell, K. Organometallics 2000, 19,
741; (d) Buchmeiser, M.; Schareina, T.; Kempe, R.; Wurst,
K. J. Organomet. Chem. 2001, 634, 39; (e) Yang, C.;
In summary, the tedicyp/palladium complex is an effi-
cient catalyst for the alkynylation of several aryl halides
with alkynols. The reactions can be performed with as
little as 0.01% catalyst with the most reactive substrates.
The rate of the reactions depends both on the aryl halide
and on the alkynol. In the presence of but-1-yn-4-ol,
pent-1-yn-5-ol and hex-1-yn-6-ol higher reaction rates
are observed with activated bromides. A lower reactivity
is generally observed with propargyl alcohol. These
results represent economically attractive procedures;
moreover, due to the high price of palladium, the
advantage of low catalyst loading reactions can become
increasingly important for industrial processes. We
believe that this system compares favourably with other
catalyst systems that have been reported for this process.
This study provides further evidence of the usefulness of
tedicyp ligand in palladium-catalysed coupling reactions.
€
Nolan, S. Organometallics 2002, 21, 1020; (f) Kollhofer,
A.; Pullmann, T.; Plenio, H. Angew. Chem., Int. Ed. 2003,
ꢁ
42, 1056; (g) Mery, D.; Heuze, K.; Astruc, D. Chem.
Commun. 2003, 1934.
ꢁ
€
7. (a) Herrmann, W. A.; Bohm, V.; Reisinger, C.-P. J.
Organomet. Chem. 1999, 576, 23; (b) Hundertmark, T.;
Littke, A.; Buchwald, S.; Fu, G. Org. Lett. 2000, 2, 1729;
(c) Batey, R. A.; Shen, M.; Lough, A. J. Org. Lett. 2002, 4,
1411; (d) Alonso, D.; Najera, C.; Pacheco, C. Tetrahedron
Lett. 2002, 43, 9365.
Acknowledgements
ꢁ ꢁ
We thank the CNRS and the ÔConseil General des
Bouches-du-Rhone, FrÕ for financial support and M.F.
ꢀ
is grateful to the Ministere de la Recherche et de la
Technologie for a grant.
^
8. For a review on the synthesis of polypodal diphenylphos-
phine ligands, see: Laurenti, D.; Santelli, M. Org. Prep.
Proc. Int. 1999, 31, 245.
ꢀ
9. Laurenti, D.; Feuerstein, M.; Pepe, G.; Doucet, H.;
Santelli, M. J. Org. Chem. 2001, 66, 1633.
10. Feuerstein, M.; Laurenti, D.; Bougeant, C.; Doucet, H.;
Santelli, M. Chem. Commun. 2001, 325.
References and notes
11. Feuerstein, M.; Doucet, H.; Santelli, M. J. Org. Chem.
2001, 66, 5923.
12. Feuerstein, M.; Berthiol, F.; Doucet, H.; Santelli, M. Org.
Biomol. Chem. 2003, 1, 2235.
1. For reviews on the palladium-catalysed reaction of aryl
halides with alkynes, see: (a) Sonogashira, K. In Metal-
Catalyzed Cross-Coupling Reactions; Diederich, F., Stang,
P. J., Eds.; Wiley-VCH: New York, 1998; (b) Brandsma,
L.; Vasilevsky, S. F.; Verkruijsse, H. D. Application of
Transition Metal Catalysts in Organic Synthesis; Springer:
Berlin, 1998; (c) Sonogashira, K. J. Organomet. Chem.
2002, 653, 46.
2. For examples of reactions using aryl halides and propargyl
alcohol: (a) Sonogashira, K.; Tohda, Y.; Hagihara, N.
Tetrahedron Lett. 1975, 16, 4467; (b) Bumagin, N. A.;
Ponomaryov, A. B.; Beletskaya, I. P. Synthesis 1984, 728;
(c) Just, G.; Singh, R. Tetrahedron Lett. 1987, 28, 5981; (d)
Alami, M.; Ferri, F.; Linstrumelle, G. Tetrahedron Lett.
1993, 34, 6403; (e) Nguyen, B. V.; Yang, Z.-Y.; Burton, D.
J. J. Org. Chem. 1993, 58, 7368; (f) Kundu, N. G.;
Mahanty, J. S.; Das, P.; Das, B. Tetrahedron Lett. 1993,
13. As a typical experiment, the reaction of 4- bromoacetoph-
enone (1.99 g, 10 mmol), but-1-yn-4-ol (1.40 g, 20 mmol),
CuI (0.10 g, 0.5 mmol) and K2CO3 (2.76 g, 20 mmol)
at 100 °C during 20 h in dry DMF (10 mL) in the presence
of cis,cis,cis-1,2,3,4-tetrakis (diphenylphosphino-methyl)-
cyclopentane/[PdCl(C3H5)]2 complex (0.01 mmol) under
argon affords the corresponding product after evaporation
and filtration on silica gel (ether/pentane: 3/7) in 95%
(1.79 g) isolated yield. 1H NMR (300 MHz, CDCl3) 7.86
(d, 2H, J ¼ 8.3 Hz), 7.46 (d, 2H, J ¼ 8.3 Hz), 3.82 (t, 2H,
J ¼ 6.2 Hz), 2.70 (t, 2H, J ¼ 6.2 Hz), 2.57 (s, 3H).
14. (a) Seiller, B.; Bruneau, C.; Dixneuf, P. H. Tetrahedron
1995, 51, 13089; (b) Gabriele, B.; Salerno, G. Chem.
Commun. 1997, 1083.