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Pl Ne ae swe Jd oo u nr no at l ao df j Cu sh te mm ai sr tgr iyn s
DOI: 10.1039/C7NJ00264E
Journal Name
ARTICLE
of the pyridine ligand during the oxidation reaction. Furthermore, a
hot filtration test of the UiO-66-NH-PC solid was performed and the
oxidation reaction stopped after the UiO-66-NH-PC ligand was
1
[a] T. Mallat and A. Baiker, Chem. Rev., 2004, 104, 3037–3058;
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3
isolated from the CH CN solution (Fig. S3). This indicated that the
UiO-66-NH-PC ligand is crucial for the reaction and that there was
no leaching of the acyl pyridine moiety. In addition, SEM image and
XRD pattern of the UiO-66-NH-PC ligand remained unvaried even
after five oxidation cycles (Fig S2 and 2c). These results clearly
demonstrate that there was no alteration in the internal UiO-66
porous structure over the aerobic oxidation process.
2
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B. L. Ryland and S. S. Stahl, Angew. Chem. Int. Ed., 2014, 53,
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824–8838.
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UiO-66-NH-PC
OH
O
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TEMPO, NMI
CH CN, Air, rt, 9 h
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ín-Matute, ACS Catal., 2015, 5, 472−479; [c] M. M. Dell’Anna,
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Hu, Dyes Pigments, 2016, 134, 155-163.
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Z. J. Huang, F. B. Li, B. F. Chen and G. Q. Yuan, Green Chem.,
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[a] K. Yamaguchi, K. Mori, T. Mizugaki, K. Ebitani and K.
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Fig. 7 UiO-66-NH-PC recycling test.
4
.Conclusions
9
I. E. Markó, P. R. Giles, M. Tsukazaki, I. Chellé-Regnaut, A.
Gautier, S. M. Brown and C. J. Urch, J. Org. Chem., 1999, 64,
2433−2439.
In summary, a picolinoyl chloride post-synthetically modified UiO-66
MOF was obtained and utilized as a solid and reusable ligand for a 10 [a] J. M. Hoover and S. S. Stahl, J. Am. Chem. Soc., 2011, 133,
selective secondary alcohol oxidation reaction. A highly efficient
aerobic oxidation system for secondary alcohols was achieved using
16901−16910; [b] J. M. Hoover and S. S. Stahl, Org. Synth.,
2013, 90, 240−250.
air as the oxidant and CuBr as the copper source. Several secondary 11 [a] M. F. Semmelhack, C. R. Schmid, D. A. Cortes and C. S.
alcohols were transformed to their corresponding ketones in high
yield under mild reaction conditions. To the best of our knowledge,
this is the very first example of secondary alcohol oxidation using a
combination of copper(I) salt, recyclable ligand and air as the
oxidant. The reaction methodology was further extended to the
oxidation of primary alcohols and benzylic compounds.
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Acknowledgements
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[a] G. F. Zhang, X. W. Han, Y. X. Luan, Y. Wang, X. Wen and C. R.
Ding, Chem. Commun., 2013, 49, 7908-7910; [b] I. E. Marko´,
P. R. Giles, M. Tsukazaki, S. M. Brown and C. J. Urch, Science,
We thank the Beijing Municipal Natural Science Foundation (Grant
No. 2172037), the National Natural Science Foundation of China
(
No. 51503016), the BUCT Fund for Disciplines Construction and
1
996, 274, 2044−2046; [c] V. Pascanu, A. Bermejo Gómez, C.
Development (No. XK1529) and Fundamental Research Funds for
the Central Universities (Grant No. FRF-TP-15-019A1).
Ayats, A. E. Platero-Prats, F. Carson, J. Su, Q. Yao, M. A .
Pericàs, X. Zou, and B. Martín-Matute, ACS Catal., 2015, 5,
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72−479; [d] T. Mitsudome, Y. Mikami, K. Ebata, T. Mizugaki, K.
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Notes and references
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[a] T. Toyao, K. Miyahara, M. Fujiwaki, T. H. Kim, S. Dohshi, Y.
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