Heterogeneous Oxidation of Allylic and Benzylic Alcohols Catalyzed by Ru-Al-Mg Hydrotalcites in the Presence of Molecular Oxygen

Journal of Organic Chemistry

Volumn 63, Issue 6, 1998, Pages 1750-1751

  Kaneda, Kiyotomi ^a   Yamashita, Toyokazu ^a   Matsushita, Tsuyoshi ^a   Ebitani, Kohki ^a  

^a OSAKA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001696542     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971965c     Document Type: Article

References (23)

1. (a) Parshall, G. W.; Ittel, S. D. Homogeneous Catalysis, 2nd ed.; John Wiley & Sons, Inc.: New York, 1992.
2. (b) Hill, C. L. Advances in Oxygenated Processes; Baumstark, A. L., Ed.; JAI Press, Inc.: London, 1988; Vol. 1, p 1.
3. (c) Hudlucky, M. Oxidations in Organic Chemistry; ACS Monograph Series; American Chemical Society: Washington, DC, 1990.
4. (d) Sheldon, R. A.; Kochi, J. K. Metal-Catalyzed Oxidations of Organic Compounds; Academic Press: London, 1981.
5. Trost, B. M. Science 1991, 254, 1471; Angew. Chem., Int. Ed. Engl. 1995, 34, 259.
6. Trost, B. M. Science 1991, 254, 1471; Angew. Chem., Int. Ed. Engl. 1995, 34, 259.
7. (a) Kaneda, K.; Fujii, M.; Morioka, K. J. Org. Chem. 1996, 61, 4503.
8. (b) Kaneda, K.; Fujie, Y.; Ebitani, K. Tetrahedron Lett. 1997, 38, 9023.
9. Cavani, F.; Trifiro, F.; Vaccari, A. Catal. Today 1991, 11, 173.
10. (a) Kaneda, K.; Ueno, S.; Imanaka, T. J. Chem. Soc., Chem. Commun. 1994, 797.
11. (b) Kaneda, K.; Ueno, S.; Imanaka, T. J. Mol. Catal. A: Chem. 1995, 102, 135.
12. (c) Kaneda, K.; Ueno, S. Heterogeneous Hydrocarbon Oxidation; Warren, B. K., Oyama, S. T., Eds.; ACS Symposium Series No. 638; American Chemical Society: Washington, DC, 1996; Chapter 22, p 300.
13. Purchased from N. E. Chemcat. Co. Ltd.
14. 2/5 XPS peak position is assigned to an oxidized ruthenium. X-ray absorption measurements on the Ru K-edge also showed the state of Ru in the hydrotalcite is a cationic form. Therefore, the Ru element in the hydrotalcite is present in an oxidized state and a possibility of metallic Ru in the hydrotalcite can be excluded.
15. 4 (7.92 Å). The d-spacing of the Ru-hydrotalcite is not related to the oxidation activity. Most of the active basic sites are probably located on the outer surface of the Ru-hydrotalcite.
16. The addition of 2,6-di-tert-butyl-p-cresol as a radical scavenger to the reaction mixture did not strongly affect the yield of cinnamaldehyde.
17. (a) Almeida, M. L. S.; Beller, M.; Wang, G.-Z.; Bäckvall, J. E. Chem. Eur. J. 1996, 2, 1553.
18. (b) Karlsson, U.; Wang, G.-Z.; Bäckvall, J. E. J. Org. Chem. 1994, 59, 1196.
19. (c) Graauw, C. F.; Peters, J. A.; Bekkum, H.; Huskens, J. H. Synthesis 1994, 1007.
20. 3 gave an extremely low yield (5%) of cinnamaldehyde.
21. The basicity of the various hydrotalcites was estimated by measurement of calorimetric heats of benzoic acid adsorption using a micro differential scanning calorimetry. (a) Miyata, S. Clays. Clay Miner. 1983, 31, 305. (b) Ueno, S.; Ebitani, K.; Okubo, A.; Kaneda, K Appl. Surf. Sci. 1997, 121/122, 366.
22. The basicity of the various hydrotalcites was estimated by measurement of calorimetric heats of benzoic acid adsorption using a micro differential scanning calorimetry. (a) Miyata, S. Clays. Clay Miner. 1983, 31, 305. (b) Ueno, S.; Ebitani, K.; Okubo, A.; Kaneda, K Appl. Surf. Sci. 1997, 121/122, 366.
23. 6) efficiently oxidized both the aromatic and aliphatic allylic alcohols under our reaction conditions. The different phenomena between the above two Ru catalysts may arise from the differences of the Ru oxidation state and/or of a dispersion of the Ru species. The origin of the unique catalytic behavior of the Ru-hydrotalcite will be discussed in a full paper based on the characterization of the Ru cations in the Brucite layer by means of XAFS together with the catalyst preparation method.