Skip to content
1887
Volume 45, Issue 1
  • ISSN: 0032-1400

Abstract

The combination of RuCl(PPh) and 2,2′,6,6′-tetramethylpiperidine N-oxyl (TEMPO) affords an efficient catalytic system for the aerobic oxidation of a variety of primary and secondary alcohols, giving the corresponding aldehydes and ketones, in > 99 per cent selectivity in all cases. This interesting catalytic system is probably based on a hydridometal mechanism, involving a ‘RuH(PPh)’-species as the active catalyst. TEMPO acts as a hydrogen transfer mediator and is regenerated by oxygen.

Loading

Article metrics loading...

/content/journals/10.1595/003214001X4511519
2001-01-01
2024-06-12
Loading full text...

Full text loading...

/deliver/fulltext/pmr/45/1/pmr0045-0015.html?itemId=/content/journals/10.1595/003214001X4511519&mimeType=html&fmt=ahah

References

  1. Sheldon R. A., and Kochi J. K.Ley S. V., Norman J., Griffith W. P., and Marsden S. P.Hudlicky M. and , “Metal Catalysed Oxidations of Organic Compounds”, Academic Press, New York, 1981; , , and , Synthesis, 1994, 639; , “Oxidations in Organic Chemistry”, ACS, Washington, DC, 1990 and references cited therein [Google Scholar]
  2. Cainelli G., and Cardillo G. and , “Chromium Oxidations in Organic Chemistry”, Springer, Berlin, 1984 [Google Scholar]
  3. Sheldon R. A., Arends I. W. C. E., and Dijksman A., and , Catal. Today, 2000, 57, 157 [Google Scholar]
  4. Noata T., Takaya H., and Murahashi S.-I., and , Chem. Rev., 1998, 98, 2599 [Google Scholar]
  5. Marko I. E., Giles P. R., Tsukaza M. M, Chellé-Regnaut I., Urch C. J., and Brown S. M., , , , and , J. Am. Chem. Soe., 1997, 119, 12661 [Google Scholar]
  6. Hinzen B., Lenz R., and Ley S. V., and , Synthesis, 1998, 977 [Google Scholar]
  7. Bleloch A., Johnson B. F. G., Ley S. V., Price A. J., Shephard D. S., and Thomas A. W., , , , and , Chem. Commun., 1999, 1907 [Google Scholar]
  8. Matsushita T., Ebitani K., and Kaneda K.Kaneda K., Yamashita T., Matsushita T., and Ebitani K., and , Chem. Commun., 1999, 265; , , and , J. Org. Chem., 1998, 63, 1750 [Google Scholar]
  9. de Nooy A. E. J., Besemer A. C., and Bekkum H. vanBobbitt J. M., and Flores M. C. L., and , Synthesis, 1999, 1153 and references cited therein; and , Heteroçycles, 1988, 27, 509 [Google Scholar]
  10. Anelli P. L., Biffi C., Montati F., and Quid S.Dijksman A., Arends I. W. C. E., and Sheldon R. A., , and , J. Org. Chem., 1987, 52, 2559; , and , Chem. Commun., 2000, 271 [Google Scholar]
  11. Jenny C.-J., Lohri B., and Schlageter M., and , European Appl. 775, 684; 1997 [Google Scholar]
  12. Cella J. A., Kelley J. A., and Kenehan E. F.Rychovsky S. D., and Vaidyanathan R., and , J. Org. Chem., 1975, 40, 1860; and , J. Org. Chem., 1999, 64, 310 [Google Scholar]
  13. Inokuchi T., Matsumoto S., Nishiyama T., and Torii S., , and , J. Org. Chem., 1990, 55, 462 [Google Scholar]
  14. Zhao M., Li J., Mano E., Song Z., Tschaen D. M., Grabowski E. J. J., and Reider P.J., , , , , and , J. Org. Chem., 1999, 64, 2564 [Google Scholar]
  15. Bolm C., Magnus A. S., and Hildebrand J. P., and , Org. Lett., 2000, 2, 1173 [Google Scholar]
  16. Semmelhack M. F., Schmid C. R., Cortês D. A., and Chou C. S., , and , J. Am. Chem. Soc, 1984, 106, 3374 [Google Scholar]
  17. Holm R.RuCl2(PPh3)3 was prepared according to: , Inorg. Synth., 1970, 12, 238 [Google Scholar]
  18. Typical procedure for the aerobic oxidation of octan-2-ol: octan-2-ol (15.0 mmol; 1.96 g), n-hexadecane (internal standard; 3.0 mmol; 0.69 g), RuCl2(PPh3)3 (0.225 mmol; 216 mg) and TEMPO (0.675 mmol; 106 mg) were dissolved in 30 ml of chlorobenzene, heated in a high-pressure reactor (10 bar) to 100°C under a continuous stream (10 ml min-1) of an oxygen-nitrogen mixture (8:92; v/v) and stirred for 7 hours. Octan-2-ol conversion and octan-2-one selectivity were determined using GC-analysis (50 m × 0.53 mm CP-Wax 52 CB column).
  19. Dijksman A., Arends I. W. C. E., and Sheldon R. A., and , Chem. Commun., 1999, 1591 [Google Scholar]
  20. Bàckvall J.-E., and Andreasson U.Trost B. M., and Kulawiec R. J. and , Tetrahedron Lett., 1993, 34, 5459; and , Tetrahedron Lett., 1991, 32, 3039 [Google Scholar]
  21. Typical procedure for isolating the product: the reaction mixture was diluted with n-hexane (to remove ruthenium) and dried over MgSO4. The resulting mixture was filtered and the solvent removed in vacuo. The product was separated from chlorobenzene using Kugelrohr distillation.
  22. Dijksman A., Arends I. W. C. E., and Sheldon R. A., and , Chem. Commun., 2000, 271 [Google Scholar]
  23. Verhoef M. J., Peters J. A., and Bekkum H. vanBolm C., and Fey T.Brunei D., Lentz P., Sutra P., Deroide B., Fajula F., and Nagy J. B., and , Stud. Surf. Sci. Catal., 1999, 125, 465; and , Chem. Commun., 1999, 1795; , , , , and , Stud. Surf. Sci. Catal., 1999, 125, 237 [Google Scholar]
  24. Dijksman A., Arends I. W. C. E., and Sheldon R. A., and , submitted to Synlett
  25. Hanyu A., Takezawa E., Sakaguchi S., and Ishii Y.Sharpless K. B., Akashi K., and Oshima K.Sasson Y., and Blum J.Murahashi S.-I., Noata T., Ito K., Maeda Y., and Taki H., , and , Tetrahedron Lett., 1998, 39, 5557; , and , Tetrahedron Lett., 1976, 29, 2503; and , Tetrahedron Lett., 1971, 24, 2167; , , , and , J. Org. Chem., 1987, 52, 4319 [Google Scholar]
  26. Karlson U., Wang G.-Z., and Bäckvall J.-E., and , J. Org. Chem., 1994, 59, 1196 [Google Scholar]
  27. Paleos C. M., and Dais P. and , J. Chem. Soc. Chem. Commun., 1977, 345 [Google Scholar]
  28. Aranyos A., Csjernyik G., Szabó K. J., and Bäckvall J.-E., , and , Chem. Commun., 1999, 351 [Google Scholar]
/content/journals/10.1595/003214001X4511519
Loading
/content/journals/10.1595/003214001X4511519
Loading

Data & Media loading...

  • Article Type: Research Article
This is a required field
Please enter a valid email address
Approval was a Success
Invalid data
An Error Occurred
Approval was partially successful, following selected items could not be processed due to error