Furthermore, we have found that nanoparticles with smaller size
were generated from the anchored palladium precursor when the
aerobic oxidation of alcohols were carried out in TFT instead
toluene. On the other hand, in the case of aerobic oxidation
reactions using supported palladium catalyst on hybrid SBA-
15, the combination of organic ligand and ordered mesoporous
channels resulted in an interesting synergistic effect enhancing
catalytic activity, preventing Pd nanoparticles agglomeration,
and enabling generation of a durable catalyst. Based on this
study, a typical reactivity and durability sequence is: 3/toluene
ª 3/TFT > 2/TFT > 2/toluene >> 1/TFT ª 1/toluene. Both
catalysts 3 and 2 show high TOFs of approximately 18150 h-1
and 7230 h-1- in the oxidation of 1-phenylethanol at 150 ◦C
under solvent-free conditions. These results may find wide
potential applications in designing other types of transition
metal nanocatalysts. Further applications of this approach
with other transition metal based nanoparticles are currently
underway in our laboratories.
Jpn., 2000, 4, 135; (s) B. A. Steinhoff, A. E. King and S. S. Stahl, J.
Org. Chem., 2006, 71, 1861.
9 (a) T. Mallat and A. Baiker, Catal. Today, 1994, 19, 274; (b) K.
Ebitani, Y. Fujie and K. Kaneda, Langmuir, 1999, 15, 1907; (c) T.
Nishimura, N. Kakiuchi, M. Inoue and S. Uemura, Chem. Commun.,
2000, 1245; (d) N. Kakiuchi, Y. Maeda, T. Nishimura and S. Uemura,
J. Org. Chem., 2001, 66, 6620; (e) N. Kakiuchi, M. Nishimura,
M. Inoue and S. Uemura, Bull. Chem. Soc. Jpn., 2001, 74, 165;
(f) K. Moroi, K. Yamaguchi, T. Hara, T. Mizugaki, K. Ebitani
and K. Kaneda, J. Am. Chem. Soc., 2002, 124, 11572; (g) K.-M.
Choi, T. Akita, T. Mizugaki, K. Ebitani and K. Kaneda, New.
J. Chem., 2003, 27, 324; (h) K. Mori, T. Hara, T. Mizugaki, K.
Ebitani and K. Kaneda, J. Am. Chem. Soc., 2004, 126, 10657;
(i) U. R. Pillai and E. Sahle-Demessie, Green Chem., 2004, 6,
161.
10 (a) Y. Uozumi and R. Nakao, Angew. Chem. Int. Ed., 2003, 42, 3810;
(b) B. Corain, K. Jerabek and P. Centomo, Angew. Chem. Int. Ed.,
2004, 43, 959; (c) Z. Hou, N. Theyssen, A. Brinkmann and W. Leitner,
Angew. Chem.Int. Ed., 2005, 44, 1346; (d) M. S. Kwon, N. Kim, C. M.
Park, J. S. Lee, K. Y. Kang and J. Park, Org. Lett., 2005, 7, 1077; (e) Z.
Hou, N. Theyssen and W. Leitner, Green Chem., 2007, 9, 127; (f) K.
Hara, S. Tayama, H. Kano, T. Masuda, S. Takakusagi, T. Kondo, K.
Uosaki and M. Sawamura, Chem. Commun., 2007, 4280; (g) For an
excellent recent study of aerobic oxidation of alcohols in supercritical
carbon dioxide using supported palladium nanoparticles on hybrid
mesoporous silica see: Z. Hou, N. Theyssen, A. Bronkmann, K.
V. Klementiev, W. Gru¨nert, M. Bu¨hl, W. Schmidt, B. Spliethoff,
B. Tesche, C. Weidenthaler and W. Leitner, J. Catal., 2008, 258,
315.
11 (a) K. Mori, T. Hara, T. Mizugaki, K. Ebitani and K. Kaneda, J.
Am. Chem. Soc., 2004, 126, 10657; (b) A. Abad, P. Concepcio´n,
A. Corma and H. Garc´ıa, Angew. Chem. Int. Ed., 2005, 44, 4066;
(c) D. I. Enache, J. K. Edwards, P. Landon, B. Solsona-Espiriu, A.
F. Carley, A. A. Herzing, M. Watanabe, C. J. Kiely, D. W. Knight
and G. J. Huchings, Science, 2006, 311, 362; (d) Y. M. A. Yamada, T.
Arakawa, H. Hocke and Y. Uozumi, Angew. Chem. Int. Ed., 2007, 46,
704; (e) H. Miyamura, R. Matsubara, Y. Miyazaki and S. Kobayashi,
Angew. Chem. Int. Ed., 2007, 46, 4151.
12 B. Karimi, S. Abedi, J. H. Clark and V. Budarin, Angew. Chem. Int.
Ed., 2006, 45, 4776.
13 P. Panster and S. Wieland, Applied Homogeneous Catalysis with
Organometallic Compounds Vol. 2 (Eds. B. Cornils, W. A. Hermann,
VCH, Weinheim, 1996, pp. 605–623.
Acknowledgements
The authors acknowledge IASBS Research Councils and Iran
National Science Foundation (INSF) for support of this work.
Notes and references
1 (a) M. Hudlicky, Oxidation in Organic Chemistry, ACS Monograph
Series; American Chemical Scociety, Washington DC, 1990; (b) R.
A. Sheldon, and J. K. Kochi, Metal Catalyzed Oxidationd of Organic
Compounds, Academic Press, New York, 1984.
2 S. V. Ley, and A. Madfin, Comprehensive Organic Synthesis, B. M.
Trost, I. Fleming, S. V. Ley, Eds.; Pergamon: Oxford, U.K., 1991;
vol. 7, pp 251–289.
3 A. Mancuso and D. Swern, Synthesis, 1981, 165.
4 (a) D. B. Dess and J. C. Martin, J. Org. Chem., 1983, 48, 4155; (b) D.
B. Dess and J. C. Martin, J. Am. Chem. Soc., 1991, 113, 7277.
5 Vision 2020 Catalysis Report (www.ccrhq.org/vision/index/
roadmaps.catrep.html).
14 (a) A. Corma and H. Garcia, Chem. Rev., 2002, 102, 3879; (b) Z. L.
Lu, E. Lindner and H. A. Mayer, Chem. Rev., 2002, 102, 3543; (c) D.
E. De Vos, M. Dams, B. F. Sels and P. A. Jacobs, Chem. Rev., 2002,
102, 3615; (d) A. P. Wight and M. E. Davis, Chem. Rev., 2002, 102,
3589; (e) J. H. Clark and D. J. Macquarrie, Chem. Commun., 1998,
853.
6 (a) For recent reviews see: R. A. Sheldon, I. W. C. E. Arend and
A. Dijksman, Catal. Today, 2000, 57, 157; (b) B. Z. Zhan and A.
Thompson, Tetrahedron, 2004, 60, 2917.
7 (a) R. A. Sheldon, Green Chem., 2000, 2, G1; (b) P. T. Anastas, L. B.
Bartlett, M. M. Kirchhoff and T. C. Williamson, Catal. Today, 2000,
55, 11.
15 B. Karimi, A. Zamani and J. H. Clark, Organometallics, 2005, 24,
4695.
16 S. Paul and J. H. Clark, Green Chem., 2003, 5, 635.
17 (a) D. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B. F.
Chmelka and G. D. Stucky, Science, 1998, 279, 548; (b) D. Zhao, Q.
Huo, J. Feng, B. F. Chmelka and G. D. Stucky, J. Am. Chem. Soc.,
1998, 120, 6024.
18 (a) A. T. Bell, Science, 2003, 299, 1688; (b) D. R. Rolison, Science,
2003, 299, 1698; (c) M. A. El-Sayed, Acc. Chem. Res., 2001, 34,
257.
19 (a) R. Narayanan and M. A. El-Sayed, J. Am. Chem. Soc., 2003, 125,
8340; (b) Y. Li, E. Boone and M. A. El-Sayed, Langmuir, 2002, 18,
4921; (c) J.-L. Bars, U. Specht, J. S. Bradley and D. G. Blackmond,
Langmuir, 1999, 15, 7621.
20 (a) A. Howard, C. E. J. Mitchell and R. G. Egdell, Surf. Sci., 2002,
515, L504; (b) A. Imre, D. L. Beke, E. Contier-Moya, I. A. Szabo
and E. Gillet, Appl. Phys. A, 2000, 71, 19.
21 (a) For recent examples of the preparation and the use of metal
nanoparticles deposited on ordered porous solids see: C. Yang, P.
Liu, Y. Ho, K. Chiu and C. Chao, Chem. Mater., 2003, 15, 275; (b) J.
Zhu, Z. Konya, V. F. Puntes, I. Kiricsi, C. X. Miao, J. W. Ager, A.
P. Alivisatos and G. A. Somorjai, Langmuir, 2003, 19, 4396; (c) J.
He, T. Kunitake and A. Nakao, Chem. Mater, 2003, 15, 4401; (d) T.
F. Baumann and J. H. Satcher, Chem. Mater., 2003, 15, 3745; (e) Y.
Guari, C. Thieuleux, D. Mehdi, C. Reye, R. J. P. Corriu, S. Gomez-
Gallardo, K. Philippot and B. Chaudret, Chem. Mater., 2003, 15,
8 (a) K. Kaneda, Y. Fujii and K. Morioka, J. Org. Chem., 1996, 61,
4502; (b) K. Kaneda, Y. Fujii and K. Ebitani, Tetrahedron Lett.,
1997, 38, 9023; (c) K. P. Peterson and R. C. Larock, J. Org. Chem.,
1998, 62, 3185; (d) T. Nishimura, T. Onoue, K. Ohe and S. Uemura,
Tetrahedron Lett., 1998, 39, 6011; (e) T. Nishimura, T. Onoue, K. Ohe
and S. Uemura, J. Org. Chem., 1999, 64, 6750; (f) G.-J. T. Brink, I.
W. C. E. Arends and R. A. Sheldon, Science, 2000, 287, 1636; (g) K.
Hallman and C. Moberg, Adv. Synth. Catal., 2001, 343, 260; (h) M.
J. Schultz, C. C. Park and M. S. Sigman, Chem. Commun., 2002,
3034; (i) D. R. Jensen, M. J. Schultz, J. A. Mueller and M. S. Sigman,
Angew. Chem. Int. Ed., 2003, 42, 3810; (j) G.-J. T. Brink, I. W. C.
E. Arends and R. A. Sheldon, Adv. Synth. Catal., 2002, 344, 355;
(k) T. Nishimura and S. Uemura, Synlett, 2004, 201; (l) S. Paavola,
K. Zetterberg, T. Privalov, I. Cso¨regh and C. Moberg, Adv. Synth.
Catal., 2004, 346, 237; (m) T. Iwasawa, M. Tokunaga, T. Obora and
Y. Tsuji, J. Am. Chem. Soc., 2004, 126, 6554; (n) M. J. Schultz, S. S.
Hamilton, D. R. Jensen and M. S. Sigman, J. Org. Chem., 2005, 70,
3343; (o) T. Iwasawa, M. Tokunaga, Y. Obora and Y. Tsuji, J. Am.
Chem. Soc., 2004, 126, 6554; (p) For a recent review on palladium
catalyzed oxidation of alcohols see: J. Muzart, Tetrahedron, 2003,
59, 5789; (q) For recent interesting reviews on palladium catalyzed
aerobic oxidations of organic chemicals see: S. S. Stahl, Angew. Chem.
Int. Ed., 2004, 43, 3400; (r) T. Nishimura and S. Uemura, Catal. Surv.
118 | Green Chem., 2009, 11, 109–119
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