Catalyst reusability for coupling of phenylacetylene with
4-chlorobenzonitrile
14 D. A. Alonso, C. Na´jera and M. C. Pacheco, Tetrahedron Lett., 2002,
43, 9365.
15 B. M. Choudary, S. Madhi, N. S. Chowdari, M. L. Kantam and B.
Sreedhar, J. Am. Chem. Soc., 2002, 124, 14127.
16 V. P. W. Bo¨hm and W. A. Herrmann, Eur. J. Org. Chem., 2000, 3679.
17 S. Urgaonkar and J. G. Verkade, J. Org. Chem., 2004, 69, 5752.
18 L. Djakovitch and P. Rollet, Adv. Synth. Catal., 2004, 346, 1782.
19 A. F. Littke and G. C. Fu, Angew. Chem., Int. Ed., 2002, 41, 4176.
20 M. Alami, B. Crousse and F. Ferri, J. Organomet. Chem., 2001, 624,
114.
For reusability studies the catalyst used in a preparative scale was
separated using a vacuum filter, washed with acetone (3 × 10 mL)
and reused after drying at 50 ◦C. All further runs were similar
to that described for the fresh catalyst. Reaction samples were
analysed by GC.
21 M. Eckhardt and G. C. Fu, J. Am. Chem. Soc., 2003, 125, 13642.
22 M. Feuerstein, H. Doucet and M. Santelli, Tetrahedron Lett., 2005, 46,
1717.
23 A. C. Hillier, G. A. Grasa, M. S. Viciu, H. M. Lee, C. L. Yang and S. P.
Nolan, J. Organomet. Chem., 2002, 653, 69.
24 T. Hundertmark, A. F. Littke, S. L. Buchwald and G. C. Fu, Org. Lett.,
2000, 2, 1729.
25 A. Ko¨llhofer, T. Pullmann and H. Plenio, Angew. Chem., Int. Ed., 2003,
42, 1056.
26 D. Gelman and S. L. Buchwald, Angew. Chem., Int. Ed., 2003, 42, 5993.
27 M. B. Thathagar, J. Beckers and G. Rothenberg, J. Am. Chem. Soc.,
2002, 124, 11858.
28 M. B. Thathagar, J. Beckers and G. Rothenberg, Adv. Synth. Catal.,
2003, 345, 979.
Pd/C catalysed ‘domino’ HALEX–Sonogashira reaction using
catalytic KI
The reaction set-up and the pre-reaction procedure were similar
to that used in the one-pot HALEX and Sonogashira reaction
performed on a preparative scale. The reactor was then charged
with Pd/C (3.0 mol%), phenylacetylene (0.41 g, 4.0 mmol), KF
(0.23 g, 4.0 mmol) and KI (0.02 g, 0.13 mmol, 5 mol%). 4-
Chlorobenzonitrile (0.36 g, 2.6 mmol) was added and the mixture
◦
was stirred at 130 C for 48 h under a slight overpressure of N2.
Reaction progress was monitored by GC.
29 (a) A. Papp, K. Miklos, M. Forgo and A. Molnar, J. Mol. Catal. A:
Chem., 2005, 229, 107; (b) J. Horniakova, T. Raja, Y. Kubota and Y.
Sugi, J. Mol. Catal. A: Chem., 2004, 217, 73; (c) A. Corma, H. Garcia,
A. Leyva and A. Primo, Appl. Catal., A, 2004, 257, 77; (d) Y. M. A.
Yamada, K. Takeda, H. Takahashi and S. Ikegami, J. Org. Chem., 2003,
68, 7733; (e) A. Biffis, M. Zecca and M. Basato, Eur. J. Inorg. Chem.,
2001, 1131; (f) R. L. Augustine and S. T. Oleary, J. Mol. Catal. A:
Chem., 1995, 95, 277; (g) D. A. Conlon, B. Pipik, S. Ferdinand, C. R.
LeBlond, J. R. Sowa, Jr., B. Izzo, P. Collins, G. J. Ho, J. M. Williams,
Y. J. Shi and Y. K. Sun, Adv. Synth. Catal., 2003, 345, 931.
30 R. G. Heidenreich, K. Ko¨hler, J. G. E. Krauter and J. Pietsch,
SYNLETT, 2002, 1118.
31 Z. Novak, A. Szabo, J. Repasi and A. Kotschy, J. Org. Chem., 2003, 68,
3327.
32 F. Quignard, S. Larbot, S. Goutodier and A. Choplin, J. Chem. Soc.,
Dalton Trans., 2002, 1147.
33 A. S. Hay, J. Org. Chem., 1962, 27, 3320.
Acknowledgements
We thank M. C. Mittelmeijer-Hazeleger for measuring the surface
area of Pd/C catalysts and for useful discussions.
References
1 K. Sonogashira, in Metal-Catalyzed Cross-Coupling Reactions, ed.
F. Diederich and P. J. Stang, Wiley-VCH, Weinheim, 1997, p. 203.
2 (a) H. F. Chow, C. W. Wan, K. H. Low and Y. Y. Yeung, J. Org. Chem.,
2001, 66, 1910; (b) I. Paterson, R. D. M. Davies and R. Marquez,
Angew. Chem., Int. Ed., 2001, 40, 603; (c) M. Toyota, C. Komori and
M. Ihara, J. Org. Chem., 2000, 65, 7110.
3 (a) U. H. F. Bunz, Chem. Rev., 2000, 100, 1605; (b) R. L. Wu, J. S.
Schumm, D. L. Pearson and J. M. Tour, J. Org. Chem., 1996, 61, 6906.
4 M. Erde´lyi and A. Gogoll, J. Org. Chem., 2001, 66, 4165.
5 N. E. Leadbeater and B. J. Tominack, Tetrahedron Lett., 2003, 44, 8653.
6 K. Okuro, M. Furuune, M. Enna, M. Miura and M. Nomura, J. Org.
Chem., 1993, 58, 4716.
7 R. K. Gujadhur, C. G. Bates and D. Venkataraman, Org. Lett., 2001,
3, 4315.
8 S. K. Kang, S. K. Yoon and Y. M. Kim, Org. Lett., 2001, 3, 2697.
9 S. Cacchi, G. Fabrizi and L. M. Parisi, Org. Lett., 2003, 5, 3843.
10 I. P. Beletskaya, G. V. Latyshev, A. V. Tsvetkov and N. V. Lukashev,
Tetrahedron Lett., 2003, 44, 5011.
34 A. Elangovan, Y. H. Wang and T. I. Ho, Org. Lett., 2003, 5, 1841.
35 S. H. Yang, C. S. Li and C. H. Cheng, J. Org. Chem., 1987, 52, 691.
36 A. Klapars and S. L. Buchwald, J. Am. Chem. Soc., 2002, 124, 14844.
37 I. Paterson, R. D. M. Davies and R. Marquez, Angew. Chem., Int. Ed.,
2001, 40, 603.
38 R. A. Bunce, Tetrahedron, 1995, 51, 13103.
39 J. J. Bozell and C. E. Vogt, J. Am. Chem. Soc., 1988, 110, 2655.
40 Y. Sasson, S. Negussie, M. Royz and N. Mushkin, Chem. Commun.,
1996, 297.
41 F. Y. Zhao and M. Arai, React. Kinet. Catal. Lett., 2004, 81, 281.
42 S. Mukhopadhyay, G. Rothenberg, D. Gitis, H. Wiener and Y. Sasson,
J. Chem. Soc., Perkin Trans. 2, 1999, 2481.
11 M. B. Thathagar, J. Beckers and G. Rothenberg, Green Chem., 2004, 6,
215.
12 D. Me´ry, K. He´uze and D. Astruc, Chem. Commun., 2003, 1934.
13 X. Fu, S. Zhang, J. Yin and D. P. Schumacher, Tetrahedron Lett., 2002,
43, 6673.
43 H. Wiener, J. Blum and Y. Sasson, J. Org. Chem., 1991, 56, 6145.
44 H. Wiener, J. Blum and Y. Sasson, J. Org. Chem., 1991, 56, 4481.
45 M. Feuerstein, H. Doucet and M. Santelli, Tetrahedron Lett., 2004, 45,
8443.
46 G. Horvath and K. Kawazoe, J. Chem. Eng. Jpn., 1983, 16, 470.
This journal is
The Royal Society of Chemistry 2006
Org. Biomol. Chem., 2006, 4, 111–115 | 1 1 5
©