Angewandte
Chemie
8
3% yield after a reaction time of 5 h (Table 6, entry 3).
TLC (2% ethyl acetate/hexane). When the reaction was complete,
the reaction mixture was treated with water (3 mL) and ethyl acetate
10 mL). The organic and aqueous layers were then separated, and
the aqueous layer was extracted with ethyl acetate (5 mL). The
combined organic solutions were washed with brine (5 mL) and water
When iodobenzene and 4-iodoanisole were treated with
benzenethiol under the same conditions for 5 h, the corre-
sponding products were obtained in 71 and 14% yield,
respectively (Table 6, entries 1 and 2). The observed decrease
in reactivity in the order 1-iodo-4-nitrobenzene > iodoben-
zene > 4-iodoanisole suggests that these reactions proceed by
oxidative addition followed by reductive elimination
(
(
5 mL) and dried with Na SO . The solvent was evaporated, and the
2 4
residue was passed through a short pad of celite to give analytically
1
pure diphenyl sulfide (176 mg, 95%) as a colorless liquid. H NMR
1
3
(CDCl
, 400 MHz): d = 7.35–7.24 ppm (m, 10H); C NMR (CDCl ,
3
3
1
00 MHz): d = 131.25, 129.41, 127.71, 127.37 ppm; MS (EI): m/z 186
(
Scheme 3).
+
[
M] .
Received: March 23, 2007
Published online: June 6, 2007
Keywords: aryl halides · CÀS coupling · nanoparticles ·
.
synthetic methods · thiols
[
1] a) D. N. Jones, Comprehensive Organic Chemistry, Vol. 3 (Eds.:
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Perkin Trans. 1 1998, 1973; e) D. J. Procter, J. Chem. Soc. Perkin
Trans. 1 1999, 641; f) D. J. Procter, J. Chem. Soc. Perkin Trans. 1
Scheme 3. Proposed reaction pathway for the CuO-nanoparticle-cata-
lyzed CÀS cross-coupling of iodobenzene with thiols in the presence
of KOH. R=alkyl, aryl.
The catalyst was found to be recyclable without loss of
activity (Table 7). After the reaction of benzenethiol with
iodobenzene had reached completion, the catalyst was
recovered from the reaction mixture by centrifugation and
2
1
001, 335; g) C. G. Frost, P. Mendonca, J. Chem. Soc. Perkin Trans.
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Chem. Ges. 1903, 36, 2382; l) J. F. Hartwig, Angew. Chem. 1998,
110, 2154; Angew. Chem. Int. Ed. 1998, 37, 2046; m) J. P. Wolfe, S.
Wagaw, J.-F. Marcoux, S. L. Buchwald, Acc. Chem. Res. 1998, 31,
Table 7: Recycling of CuO nanoparticles.
805.
[
2] a) J. Lindley, Tetrahedron 1984, 40, 1433; b) T. Yamamoto, Y.
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DIBAL-H = diisobutylaluminum hydride.
Run
Catalyst
recovery [%]
Product
yield [%]
[
[
[
a]
b]
b]
1
2
3
96
93
88
95
89
81
[3] a) T. Migita, T. Shimizu, Y. Asami, J. Shiobara, Y. Kato, M.
Kosugi, Bull. Chem. Soc. Jpn. 1980, 53, 1385; b) M. Kosugi, T.
Ogata, M. Terada, H. Sano, T. Migita, Bull. Chem. Soc. Jpn. 1985,
5
8, 3657.
[
a] CuO nanoparticles (1.26 mol%), benzenethiol (1 mmol), iodoben-
zene (1.1 mmol), KOH (1.5 mmol), and DMSO (1 mL) were stirred for
0 hat 80 8C under a nitrogen atmosphere. [b] The recovered catalyst
[
4] a) C. Mispelaere-Canivet, J.-F. Spindler, S. Perrio, P. Beslin,
Tetrahedron 2005, 61, 5253; b) T. Itoh, T. Mase, Org. Lett. 2004, 6,
4
Am. Chem. Soc. 2006, 128, 2180; d) M. Murata, S. L. Buchwald,
Tetrahedron 2004, 60, 7397; e) U. Schopfer, A. Schlapbach,
Tetrahedron 2001, 57, 3069; f) G. Y. Li, Angew. Chem. 2001, 113,
1
587; c) M. A. Fernandez Rodr y´ guez, Q. Shen, J. F. Hartwig, J.
was used under identical reaction conditions to those for the first run.
reused up to three times. Only a slight decrease in catalytic
activity was observed.
1
561; Angew. Chem. Int. Ed. 2001, 40, 1513; g) R. S. BarbiØri,
C. R. Bellato, A. K. C. Dias, A. C. Massabni, Catal. Lett. 2006,
109, 171; h) M. J. Dickens, J. P. Gilday, T. J. Mowlem, D. A.
Widdowson, Tetrahedron 1991, 47, 8621; i) T. Ishiyama, M. Mori,
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Volante, J. Org. Chem. 1998, 63, 9606; k) G. Mann, D. Baranano,
J. F. Hartwig, A. L. Rheingold, I. A. Guzei, J. Am. Chem. Soc.
In conclusion, we have described the CÀS cross-coupling
of thiols with iodobenzene in the presence of relatively
inexpensive air-stable CuO nanoparticles. A variety of thiols
could be cross-coupled with iodobenzene in this simple and
efficient reaction to give the desired products in high yields.
We are currently pursuing the further application of this
procedure.
1
998, 120, 9205.
[5] a) H. J. Cristau, B. Chabaud, A. Chene, H. Christol, Synthesis
981, 892; b) C. Millois, P. Diaz, Org. Lett. 2000, 2, 1705; c) V.
1
Percec, J.-Y. Bae, D. H. Hill, J. Org. Chem. 1995, 60, 6895; d) K.
Takagi, Chem. Lett. 1987, 2221.
Experimental Section
[6] a) C. G. Bates, R. K. Gujadhur, D. Venkataraman, Org. Lett.
2002, 4, 2803; b) F. Y. Kwong, S. L. Buchwald, Org. Lett. 2002, 4,
3517; c) Y.-J. Wu, H. He, Synlett 2003, 1789; d) C. G. Bates, P.
Saejueng, M. Q. Doherty, D. Venkataraman, Org. Lett. 2004, 6,
5005; e) W. Deng, Y. Zou, Y.-F. Wang, L. Liu, Q.-X. Guo, Synlett
Typical Procedure: A mixture of iodobenzene (223 mg, 1.1 mmol),
benzenethiol (110 mg, 1 mmol), CuO nanoparticles (1.08 mg,
1
.26 mol%), and KOH (84 mg, 1.5 mmol) was stirred at 808C under
N in DMSO (1 mL). The progress of the reaction was monitored by
2
Angew. Chem. Int. Ed. 2007, 46, 5583 –5586
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5585