S. Sahoo et al. / Journal of Catalysis 254 (2008) 91–100
99
with a substrate-to-catalyst ratio 30 times higher than that used
in the previously reported monodentate ligand-based catalytic
systems. The catalyst was reused at least five times, and main-
tained the same activity and selectivity. Thus, we consider this
protocol to be a readily accessible pathway to highly enantios-
elective immobilized hydrogenation catalysts.
Acknowledgment
S.S. thanks CSIR, New Delhi, for the award of a research
fellowship.
References
[
[
1] M.T. Reetz, G. Mehler, Angew. Chem. Int. Ed. 39 (2000) 3889.
2] M. Berg, A.J. Minnaard, E.P. Schudde, J. Esch, A.H.M. de Vries, J.G. de
Vries, B.L. Feringa, J. Am. Chem. Soc. 122 (2000) 11539.
[3] C. Claver, E. Fernandez, A. Gillon, K. Heslop, D.J. Hyett, A. Martorell,
A.G. Orpen, P.G. Pringle, Chem. Commun. (2000) 961.
[
[
4] I.V. Komaro, A. Börner, Angew. Chem. Int. Ed. 40 (2001) 1197.
5] M.T. Reetz, A. Meiswinkel, G. Mehler, K. Angermund, M. Graf, W. Thiel,
R. Mynott, D.G. Blackmond, J. Am. Chem. Soc. 127 (2005) 10305.
6] J.M. Thomas, W.J. Thomas (Eds.), Principles and Practice of Heteroge-
neous Catalysis, Wiley–VCH, Weinheim, 1997, p. 13.
[
[
7] M.D. Jones, R. Raja, J.M. Thomas, B.F.G. Johnson, D.W. Lewis,
J. Rouzard, K.D.M. Harris, Angew. Chem. Int. Ed. 42 (2003) 4326.
8] C.E. Song, D.H. Kim, D.S. Choi, Eur. J. Inorg. Chem. (2006) 2927.
9] D.E. Bergbreiter, Chem. Rev. 102 (2002) 3345.
[
[
[
[
10] N.E. Leadbeater, M. Marco, Chem. Rev. 102 (2002) 3217.
11] G.E. Oosterom, J.N.H. Reek, P.C.J. Kamer, P.W.N.M. Van Leeuwen,
Angew. Chem. Int. Ed. 40 (2001) 1828.
[
[
[
[
12] M. Heitbaum, F. Glorius, I. Escher, Angew. Chem. Int. Ed. 45 (2006) 4732.
13] C. Jakel, R. Paciello, Chem. Rev. 106 (2006) 2912.
14] P. Barbaro, Chem. Eur. J. 12 (2006) 5666.
15] C. Simons, U. Hanefeld, I.W.C.E. Arends, J.M. Adriaan, T. Maschmeyer,
R.A. Sheldon, Chem. Commun. (2004) 2830.
Fig. 9. Effect of H pressure (a) conversion of dimethylitaconate and (b) enan-
2
tiomeric excess of dimethylmethylsuccinate. Reaction conditions: 10 mmol
of the substrate, substrate to catalyst molar ratio = 1660:1, dichloromethane
◦
5
0 ml, temperature 40 C, time 20 h.
[
[
[
16] C. Simons, U. Hanefeld, I.W.C.E. Arends, T. Maschmeyer, R.A. Sheldon,
J. Catal. 239 (2006) 212.
Table 4
17] X.P. Hu, J.D. Huang, Q.H. Zengab, Z. Zheng, Chem. Commun. (2006)
Recyclability of IrPSSBA-15 in the enantioselective hydrogenation of dimeth-
293.
a
ylitaconate
18] S. Doherty, E.G. Robins, I. Pal, C.R. Newman, C. Hardacre, D. Rooney,
D.A. Mooney, Tetrahedron Asymmetry 14 (2003) 1517.
b
Entry
Cycle
Conversion
mol%)
ee
(
(%)
[19] C.E. Song, S. Lee, Chem. Rev. 102 (2002) 3495.
[
20] Q.H. Fan, Y.M. Li, A.S.C. Chan, Chem. Rev. 102 (2002) 3385.
1
2
3
4
5
6
Fresh
1st
2nd
3rd
4th
99
99
99
99
97
96
94
94
94
94
94
94
[21] D.E.D. Vos, M. Dams, B.F. Sels, P.A. Jacobs, Chem. Rev. 102 (2002)
3615.
[
22] F. Giacomina, A. Meetsma, L. Panella, L. Lefort, A.H.M. Vries, J.G.
Vries, Angew. Chem. Int. Ed. 46 (2007) 1497.
[
[
23] T. Morimoto, M. Chiba, K. Achiwa, Tetrahedron Lett. 31 (1990) 261.
24] H. Heitsch, R. Henning, H.W. Kleemann, W. Linz, W.U. Nickel, D. Rup-
pert, H. Urbach, A. Wagner, J. Med. Chem. 36 (1993) 2788.
5th
a
Reaction conditions: 10 mmol of the substrate, substrate to catalyst molar
◦
ratio = 1660:1, dichloromethane 50 ml, temperature 40 C, 20 bar H , time
[25] T. Joseph, M. Hartmann, S. Ernst, S.B. Halligudi, J. Mol. Catal. A
Chem. 207 (2004) 131.
2
2
0 h, after each cycle the catalyst was filtered and washed repeatedly with
dichloromethane, dried under vacuum and used in the next cycle.
b
[26] J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D.
Schmitt, C.T.W. Chu, D.H. Olson, E.W. Sheppard, S.B. McCullen, J.B.
Higgins, J.L. Schlenker, J. Am. Chem. Soc. 114 (1992) 10834.
%
ee was calculated by GC analysis using HP-Chiral column.
[
27] D.Y. Zhao, J.L. Feng, Q.S. Huo, N. Melosh, G.H. Fredrickson, B.F.
Chmelka, G.D. Stucky, Science 279 (1998) 548.
from inexpensive S-binol in fewer steps. Catalyst diagnosis
demonstrated the successful incorporation of ligand and metal
complex onto the mesoporous silica. Among the catalysts inves-
tigated, iridium complex immobilized over SBA-15 (IrPSSBA-
[
28] K. Nakamoto (Ed.), Infrared and Raman Spectra of Inorganic and Coordi-
nation Compounds, Part A: Theory and Applications in Inorganic Chem-
istry, Wiley, 1997, p. 266.
[29] A. Gosh, R. Kumar, J. Catal. 228 (2004) 386.
1
5) was found to be the ideal heterogeneous catalyst system
[30] T. Jerphagon, J.L. Renaud, C. Bruneau, Tetrahedron Asymmetry 15 (2004)
for the enantioselective hydrogenation of itaconic acid deriva-
tives. High conversions (99%) and excellent enantioselectivities
2101.
[31] T. Jerphagnon, J.L. Renaud, P. Demochaux, A. Ferreira, C. Bruneau, Adv.
(
up to 94% ee) were observed under milder reaction conditions
Synth. Catal. 346 (2004) 33.