Modified mesoporous silicate MCM-41 materials: immobilised perruthenate—a new highly active heterogeneous oxidation catalyst for clean organic synthesis using molecular oxygen

Abstract

A new oxidation catalyst containing perruthenate immobilised within MCM-41 has been prepared and used in the clean oxidation of alcohols to carbonyl compounds with molecular oxygen.

References

1. R. Lenz and S. V. Ley, J. Chem. Soc., Perkin Trans. 1, 1997, 3291.
2. I. E. Mark, P. R. Giles, M. Isukazaki, C. J. Urch and S. M. Brown, J. Am. Chem. Soc., 1997, 119, 12 661.
3. S. V. Ley, J. Norman, W. P. Griffith and S. P. Marsden, Synthesis, 1994, 640.
4. B. Hinzen and S. V. Ley, J. Chem. Soc., Perkin Trans. 1, 1997, 1907; B. Hinzen, R. Lenz and S. V. Ley, Synthesis, 1998, 977.
5. Several reviews considering various aspects of MCM-41 other mesoporous materials have appeared: J. Y. Ying, C. P. Mehnert and M. S. Wong, Angew. Chem., Int Ed., 1999, 38, 56; S. Biz and M. L. Occelli, Catal. Rev. Sci. Eng., 1998, 40, 329; K. Moller and T. Bein, Chem. Mater., 1998, 10, 2950; A. Corma, Top. Catal., 1997, 4, 249; G. D. Stucky, Q. Huo, A. Firouzi, B. F. Chmelka, S. Schacht, I. G. Voigt-Martin and F. Schuth, in Progress in Zeolite and Microporous Materials, Studies in Surface Science and Catalysis, Vol 105, ed. H. Chon, S.-K. Ihm, Y. S. Uh, Elsevier, Amsterdam, 1997, 3; C. J. Brinker, Curr. Opin Solid State Mater. Sci., 1996, 1, 798; N. K. Raman, M. T. Anderson and C. J. Brinker, Chem. Mater., 1996, 8, 1682; D. M. Antonelli and J. Y. Ying, Curr. Opin. Colloid Interface Sci., 1996, 1, 523; P. Behrens, Angew. Chem., Int. Ed. Engl., 1996, 35, 515; X. S. Zhao, G. Q. Lu and G. J. Millar, Ind. Eng. Chem. Res., 1996, 35, 2075; A. Sayari, Chem. Mater., 1996, 8, 1840.
6. For different methods of tethering chiral catalysts, see D. E. De Vos, S. De Wildemann, B. F. Sels, P. J. Grobet and P. A. Jacobs, Angew. Chem., Int. Ed., 1999, 38, 980; B. F. G. Johnson, S. A. Raynor, D. S. Shephard, T. Maschmeyer, J. M. Thomas, G. Sankar, S. Bromley, R. D. Oldroyd, L. Gladden and M. D. Mantle, Chem. Commun., 1999, 1167.
7. D. S. Shephard, W. Zhou, T. Maschmeyer, J. M. Matters, C. L. Roper, S. Parsons, B. F. G. Johnson and M. J. Duer, Angew. Chem., Int. Ed., 1998, 37, 2719; T. Maschmeyer, R. D. Oldroyd, G. Sankar, J. M. Thomas, I. J. Shannon, J. A. Klepetko, A. F. Masters, J. K. Beattie and C. R. A. Catlow, Angew. Chem., Int. Ed. Engl., 1997, 36, 1639; J. Liu, X. Feng, G. E. Fryxell, L.-Q. Wang, A. Y. Kim and M. Gong, Adv. Mater., 1998, 10, 161.
8. 10 wt% of the solid catalyst 3 corresponds to 0.3 wt% Ru by ICP analysis.
9. 10 wt% of the solid catalyst 6 corresponds to 1.1 wt% Ru by ICP analysis.
10. General procedure for the oxidation of alcohols: To a solution of the alcohol (30.0 mg) in dry toluene (5 cm³) was added MCMSP 6(3.0 mg) and the resulting mixture heated at 80 °C, for 30 min to 3 h in an oxygen atmosphere. After cooling, filtration of the mixture followed by evaporation of the solution afforded the pure aldehyde in quantitative yield (Table 1). The solid catalytic oxidant reagent can be re-used many times (up to 12 times without loss of activity). It can be easily filtered through a polypropylene filter or through a bond elut cartridge and then washed off the surface with toluene. In addition, recovery by centrifugation was also found to be quantitative.
11. J. Habermann, S. V. Ley and J. S. Scott, J. Chem. Soc., Perkin Trans. 1, 1999, 1253.
12. D. S. Shephard, G. Sankar, J. M. Thomas, D. Ozkaya, B. F. G. Johnson, R. Raja, R. D. Oldroyd and R. G. Bell, Chem. Eur. J., 1998, 4, 1214.
13. In experiments (i) and (iv), no oxidation was observed after 50 h, in toluene/oxygen at 80 °C, implying that a perruthenate derived species was responsible for the catalysis and not RuO₂. In experiments (i) and (iii), approximately 10 and 70% oxidation, respectively, to the aldehyde was observed after 3 days under the same conditions and complete leaching of potassium perruthenate was observed in both cases. The used solid material from experiments (ii) and (iii) showed no catalytic oxidative activity when reused.
14. D. G. Lee, Z. Wang and W. D. Chandler, J. Org. Chem., 1992, 57, 3276.
15. B. Hinzen and S. V. Ley, J. Chem. Soc., Perkin Trans. 1, 1998, 1; F. Haunert, M. H. Bolli, B. Hinzen and S. V. Ley, J. Chem. Soc., Perkin Trans. 1, 1998, 2235; S. V. Ley, M. H. Bolli, B. Hinzen, A.-G. Gervois and B. J. Hall, J. Chem. Soc., Perkin Trans. 1, 1998, 2239; M. H. Bolli and S. V. Ley, J. Chem. Soc., Perkin Trans. 1, 1998, 2243; J. Habermann, S. V. Ley and J. S. Scott, J. Chem. Soc., Perkin Trans. 1, 1998, 3127; M. Caldarelli, J. Habermann and S. V. Ley, J. Chem. Soc., Perkin Trans. 1, 1999, 107; S. V. Ley, A. W. Thomas and H. Finch, J. Chem. Soc., Perkin Trans. 1, 1999, 669; S. V. Ley, O. Schucht, A. W. Thomas and P. J. Murray, J. Chem. Soc., Perkin Trans. 1, 1999, 1251.