Organic Letters
Letter
Surprisingly, the coupling of phenol proved difficult in
toluene, giving diphenyl ether 3h in very low yields. However,
performing the reaction in DMF restored the reactivity and
allowed to isolate 3h in good to high yields. Less surprisingly,
diaryl ethers 3i and 3j could not be formed from respectively
the electron-poor 4-cyano- and 4-nitrophenols, even in DMF as
solvent or at higher temperatures. These results were in line
with previous works reporting the ineffectiveness of electron-
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24
poor substrates in Ullmann-type coupling.
In contrast, more electron-rich phenols fortunately proved to
be better coupling partners, and diaryl ethers 3k and 3l were
efficiently obtained from p-cresol and 2,3,5-trimethylphenol,
respectively. The more hindered 2,4,6-trimethylphenol gave the
corresponding diaryl ether 3m in a satisfactory yield, especially
with bromobenzene as coupling partner.
(
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In conclusion, we have shown that the copper(I)-exchanged
(
I
zeolite Cu −USY can efficiently catalyze the Ullmann-type
1
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synthesis of diaryl ethers under ligand-free conditions. In
addition, the catalyst can be easily recovered and recycled up to
five times without dramatic loss of activity. Further work is now
3
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I
underway in our groups in order to extend the use of Cu −USY
(
13) (a) Zhang, P.; Yuan, J.; Li, H.; Liu, X.; Xu, X.; Antonietti, M.;
as a catalyst in other relevant C−C, C−N, and C−S coupling
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5
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ASSOCIATED CONTENT
Supporting Information
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*
S
(
(
Ouazzani, F. Adv. Synth. Catal. 2008, 350, 2205−2208. (c) Benyahya,
S.; Monnier, F.; Wong Chi Man, M.; Bied, C.; Ouazzani, F.; Taillefer,
M. Green Chem. 2009, 11, 1121−1123.
Full experimental details and characterization data for all
products as well as their H, DEPT, and C NMR
(
15) (a) Zhang, J.; Zhang, Z.; Wang, Y.; Zheng, X.; Wang, Z. Eur. J.
1
13
Org. Chem. 2008, 2008, 5112−5116. (b) Kim, J. K.; Park, J. C.; Kim,
A.; Kim, A. Y.; Lee, H. J.; Song, H.; Park, K. H. Eur. J. Inorg. Chem.
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AUTHOR INFORMATION
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*
*
(16) Phan, N. T. S.; Nguyen, T. T.; Nguyen, C. V.; Nguyen, T. T.
Appl. Catal., A 2013, 457, 69−77.
Notes
(
17) (a) Chassaing, S.; Alix, A.; Boningari, T.; Sani Souna Sido, A.;
Keller, M.; Kuhn, P.; Louis, B.; Pale, P.; Sommer, J. Synthesis 2010,
010, 1557−1567. (a) Chassaing, S.; Alix, A.; Olmos, A.; Keller, M.;
Sommer, J.; Pale, P. Z. Naturforsch., B: J. Chem. Sci. 2010, 65, 783−790.
18) (a) Chassaing, S.; Kumarraja, M.; Sani Souna Sido, A.; Pale, P.;
2
The authors declare no competing financial interest.
(
Sommer, J. Org. Lett. 2007, 9, 883−886. (b) Chassaing, S.; Sani Souna
ACKNOWLEDGMENTS
This work was supported by the Agence Nationale de la
Recherche (ANR-13-BS07-0017-02 ChOZe) and the CNRS.
■
Sido, A.; Alix, A.; Kumarraja, M.; Pale, P.; Sommer, J. Chem. - Eur. J.
2
008, 14, 6713−6721. (c) Alix, A.; Chassaing, S.; Pale, P.; Sommer, J.
Tetrahedron 2008, 64, 8922−8929.
We thank Eric Wimmer and Doctor Valer
́
ie Ben
́
et
́
eau
(19) Keller, M.; Sido, A.S. S.; Pale, P.; Sommer, J. Chem. - Eur. J.
2009, 15, 2810−2817.
(
LASYROC, Universite de Strasbourg) for preparation of the
́
zeolitic materials.
(20) Ben
Tetrahedron Lett. 2010, 51, 3673−3677.
21) (a) Kuhn, P.; Alix, A.; Kumarraja, M.; Louis, B.; Pale, P.;
́ ́
eteau, V.; Olmos, A.; Boningari, T.; Sommer, J.; Pale, P.
(
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