can play a major role in catalysis of epoxidation, since it seems
likely that its role will be to transfer only one of its O-atoms,
leaving a molecule of the allylic alcohol. The very high epoxide
selectivities attainable in these systems would seem to preclude
a catalytic cycle involving the hydroperoxide. On the basis of the
present data, we can only speculate about the detailed course of
the reaction. We plan further experimental studies to test these
mechanistic proposals.
11 T. A. Nijhuis, T. Visser and B. M. Weckhuysen, Angew. Chem., Int.
Ed., 2005, 44, 1115.
1
1
2 T. A. Nijhuis and B. M. Weckhuysen, Chem. Commun., 2005, 6002.
3 N. Yap, R. P. Andres and W. N. Delgass, J. Catal., 2004, 226, 156.
14 A. Zwijnenburg, M. Makkee and J. A. Moulijn, Appl. Catal. A, 2004,
270, 49.
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
5 C. Qi, T. Akita, M. Okumura, K. Kuraoka and M. Haruta, Appl.
Catal. A, 2003, 253, 75.
6 B. Taylor, J. Lauterbach and W. N. Delgass, Appl. Catal. A, 2005,
291, 188.
7 A. K. Sinha, S. Seelan, M. Okumura, T. Akita, S. Tsubota and M.
Haruta, J. Phys. Chem. B, 2005, 109, 3956.
Conclusions
8 B. Chowdhury, J. J. Bravo-Suarez, M. Date, S. Tsubota and M.
Haruta, Angew. Chem., Int. Ed., 2006, 45, 412.
We have shown that gold supported on graphite is a very
promising catalyst for the epoxidation of cylcooctene using
catalytic amounts of an added hydroperoxy species. The catalyst
is effective under mild, solvent-free conditions using oxygen
from air as the oxidant. Selectivities to the epoxide can be greater
than 80% and we consider that with appropriate catalyst design
further enhancements inactivity and selectivity can be expected.
9 E. Sacaliuc, A. M. Beale, B. M. Weckhuysen and T. A. Nijhuis,
J. Catal., 2007, 248, 235.
0 J. Lu, X. Zhang, J. J. Bravo-Su a´ rez, K. K. Bando, T. Fujitani and
S. T. Oyama, J. Catal., 2007, 250, 350.
1 A. K. Sinha, S. Seelan, S. Tsubota and M. Haruta, Angew. Chem.,
Int. Ed., 2004, 43, 1546.
2 J. K. Edwards and G. J. Hutchings, Angew. Chem., Int. Ed., 2008, 47,
9
192.
3 N. S. Patil, B. S. Uphade, P. Jana, S. K. Bhargava and V. R.
Choudhary, Chem. Lett., 2004, 33, 400.
4 N. S. Patil, B. S. Uphade, D. G. McCulloh, S. K. Bhargava and V. R.
Choudhary, Catal. Commun., 2004, 5, 681.
5 N. S. Patil, B. S. Uphade, P. Jana, S. K. Bharagava and V. R.
Choudhary, J.Catal., 2004, 223, 236.
6 N. S. Patil, R. Jha, B. S. Uphade, S. K. Bhargava and V. R. Choudhary,
Appl. Catal.,A, 2004, 275, 87.
Acknowledgements
This work formed part of an EPSRC funded project and we
thank them for funding this research. We also thank King
Abdul Aziz University (Saudi Arabia Government) for financial
support. We thank a referee for helpful comments.
7 N. S. Patil, B. S. Uphade, P. Jana, R. S. Sonawane, S. K. Bhargava
and V. R. Choudhary, Catal. Lett., 2004, 94, 89.
8 D. Yin, L. Qin, J. Liu, C. L. and Y. Jin, J. Molec. Catal. A, 2005, 240,
4
0.
References
9 M. D. Hughes, Y.-J. Xu, P. Jenkins, P. McMorn, P. Landon, D. I.
Enache, A. F. Carley, G. A. Attard, G. J. Hutchings, F. King, E. H.
Stitt, P. Johnston, K. Griffin and C. J. Kiely, Nature, 2005, 437, 1132.
1
2
R. A. Sheldon, Stud. Surf. Sci. Catal., 1991, 66, 33.
R. M. Lambert, F. J. Williams, R. L. Cropley and A. Palermo,
J. Molec. Catal., 2005, 228, 27.
30 P. Lignier, F. Morfin, S. Mangematin, L. Massin, J.-L. Rousset and
V. C ap s , Chem. Commun., 2007, 186.
31 P. Lignier, S. Mangematin, F. Morfin, J.-L. Rousset and V. Caps,
Catal. Today., 2008, 138, 50.
32 P. Lignier, F. Morfin, Laurent Piccolo, J.-L. Rousset and V. Caps,
Catal. Today., 2007, 122, 284.
3
E. Klemm, E. Dietzsch, T. Schwarz, T. Kruppa, A. Lange de Oliveira,
F. Becker, G. Markowz, S. Schirrmeister, R. Sch u¨ tte, K. J. Caspary,
F. Sch u¨ th and D. H o¨ nicke, Ind. Eng. Chem. Res., 2008, 47, 2086.
C. Della Pina, E. Falletta, L. Prati and M. Rossi, Chem. Soc. Rev.,
4
2
008, 37, 2077.
5
6
7
T. Hayashi, K. Tanaka and M. Haruta, J. Catal., 1998, 178, 566.
M. Haruta and M. Date, Appl. Catal. A, 2001, 222, 427.
33 X. Deng and C. M. Friend, J. Amer. Chem. Soc., 2005, 127, 17178.
34 M. Turner, V. B. Golovko, O. P. H. Vaughan, P. Abdulkin, A.
Berenguer-Murcia, M. S. Tikhov, B. F. G. Johnson and R. M.
Lambert, Nature, 2008, 454, 981.
35 J. Branderup, E. H. Immergut, and E. A. Grulke, Polymer Handbook,
4th Ed., John Wiley, New York, 1999, 11, 2.
36 L. Prati and M. Rossi, J. Catal., 1998, 176, 552.
37 J. A. Lopez-Sanchez, N. Dimitratos, P. Miedziak, E. Ntainjua, J. K.
Edwards, D. Morgan, A. F. Carley, R. Tiruvalam, C. J. Kiely and
G. J. Hutchings, Phys. Chem. Chem. Phys., 2008, 10, 1921.
T. A. Nijhuis, T. Visser and B. M. Weckhuysen, J. Phys. Chem. B,
2
005, 109, 19309.
8
9
B. S. Uphade, S. Tsubota, T. Hayashi and M. Haruta, Chem. Lett.,
1
998, 1277.
T. A. Nijhuis, B. J. Huizinga, M. Makkee and J. A. Moulijn, Ind. Eng.
Chem. Res., 1999, 38, 884.
1
0 T. A. Nijhuis, T. Q. Gardner and B. M. Weckhuysen, J. Catal., 2005,
36, 153.
2
1
044 | Green Chem., 2009, 11, 1037–1044
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