Skip to main content
SpringerLink
Log in

Oxidation with the “H2O2-managanese(IV) complex-carboxylic acid” reagent

1. Oxidation of saturated hydrocarbons with peroxy acids and hydrogen peroxide

  • Physical Chemistry
  • Published:
Russian Chemical Bulletin Aims and scope

Abstract

The complex [LMnIV(O)3MnIVL](PF6)2 (1), where L is 1,4 7-trimethyl-1,4,7-triazacyclononane, catalyzes a highly efficient stereoselective oxygenation of saturated hydrocarbons in the presence of H2O2. A carboxylic acid is an obligatory component of the reaction mixture, while acetonitrile or acetone can be used as solvent. The reaction occurs, forming alkyl hydroperoxide, ketone, and alcohol. Substitution at the tertiary carbon atom proceeds more easily than that at the secondary carbon atom, whereas primary C−H bonds are rather inactive. Oxidation of alkanes and alcohols with peroxy acids catalyzed by complex 1 occurs with lower efficiency.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. A. E. Shilov and G. B. Shul'pin,Chem. Rev., 1997,97, 2879.

    Article  CAS  Google Scholar 

  2. A. E. Shilov and G. B. Shul'pin,Aktivatsiya i kataliticheskie reaktsii uglevodorodov [Activation and Catalytic Reactions of Hydrocarbons], Nauka, Moscow, 1995 400 pp. (in Russian).

    Google Scholar 

  3. J. March,Advanced Organic Chemistry, J. Wiley and Sons, New York, 1992, p. 826.

    Google Scholar 

  4. J. Fossey, D. Lefort, M. Massoudi, J.-Y. Nedelec, and J. Sobra,Can. J. Chem., 1985,63, 678.

    Article  CAS  Google Scholar 

  5. A. Bravo, H.-R. Bjorsvik, F. Fontana, F. Minisci, and A. Serri,J. Org. Chem., 1996,61, 9409.

    Article  CAS  Google Scholar 

  6. R. D. Bach, C. Canapa, J. E. Winter, and P. E. Blanchette,J. Org. Chem., 1997,62, 5191.

    Article  CAS  Google Scholar 

  7. A. P. James, R. A. W. Johnstone, M. McCarron J. P. Sankey, and B. Trenbirth,J. Chem. Soc., Chem. Commun., 1998, 429.

  8. D. Tetard and J.-B. Verlhac,J. mol. Catal., A: Chem., 1996,113, 223.

    Article  CAS  Google Scholar 

  9. S. V. Barkanova, V. M. Derkacheva, O. V. Dolotova, V. D. Li, V. M. Negrimovsky, O. L. Kaliya, and E. A. Luk'yanets,Tetrahedron Lett., 1996,37, 1637.

    Article  CAS  Google Scholar 

  10. S. Banfi, M. Cavazzini, F. Coppa, S. V. Barkanova, and O. L. Kaliya,J. Chem. Soc., Perkin Trans., 2, 1997, 1577.

    Google Scholar 

  11. M. Yamaguchi, H. Kousaka, and T. Yamagishi,Chem. Lett., 1997, 769.

  12. J. T. Groves, J. Lee, and S. S. Marla,J. Am. Chem. Soc., 1997,119, 6269.

    Article  CAS  Google Scholar 

  13. R. Fish, R. H. Fong, J. B. Vincent, and G. Christou,J. Chem. Soc., Chem. Commun., 1988, 1504.

  14. K. L. Taft, R. J. Kulawiec, J. E. Sarneski, and R. H. Crabtree,Tetrahedron Lett., 1989,30, 5689.

    Article  CAS  Google Scholar 

  15. J. E. Sarneski, D. Michos, H. H. Thorp, M. Didiuk, T. Poon, J. Blewitt, G. W. Brudvig, and R. H. Crabtree,Tetrahedron Lett., 1991,32 1153.

    Article  CAS  Google Scholar 

  16. S. Banfi, F. Montanari, G. Pozzi, and S. Quici,Tetrahedron, 1994,50, 9025.

    Article  Google Scholar 

  17. S. Menage, M.-N. Colomb-Dunand-Sauthier, C. Lambeaux, and M. Fontecave,J. Chem. Soc., Chem. Commun., 1994, 1885.

  18. J. M. Vincent, S. Menage, C. Lambeaux, and M. Fontecave,Tetrahedron Lett., 1994,35, 6287.

    Article  CAS  Google Scholar 

  19. P. A. Ganeshpure, G. L. Tembe, and S. Satish,Tetrahedron. Lett., 1995,36, 8861.

    Article  CAS  Google Scholar 

  20. D. Feichtinger and D. A. Plattner,Angew. Chem. Int. Ed. Engl., 1997,36, 1718.

    Article  CAS  Google Scholar 

  21. T. Linker,Angew. Chem. Int. Ed. Engl., 1997,36, 2060.

    Article  CAS  Google Scholar 

  22. S. B. Ogunwumi and T. Bein,J. Chem. Soc., Chem. Commun., 1997, 901.

  23. J. Limburg, G. W. Brudwig, and R. H. Crabtree,J. Am. Chem. Soc., 1997,119, 2761.

    Article  CAS  Google Scholar 

  24. G. L. Tembe, P. A. Ganeshpure, and S. Satish,J. Mol. Catal. A: Chem., 1997,121, 17.

    Article  CAS  Google Scholar 

  25. F. Torrens,J. Mol. Catal., A: Chem., 1997,119, 393.

    Article  CAS  Google Scholar 

  26. M. Hirano, S. Yakabe, H. Monobe, and T. Morimoto,Can. J. Chem., 1997,75, 1905.

    Article  CAS  Google Scholar 

  27. M. Palucki, N. S. Finney, P. J. Pospisil, M. L. Güler, T. Ishida, and E. N. Jacobsen,J. Am. Chem. Soc., 1998,120 948.

    Article  CAS  Google Scholar 

  28. C. Quee-Smith, L. DelPizzo, S. H. Jureller, and J. L. Kerschner,Inorg. Chem., 1996,35, 6461.

    Article  CAS  Google Scholar 

  29. R. Hage,Rect. Trav. Chim. Pays-Bas, 1996,115, 385.

    CAS  Google Scholar 

  30. D. E. De Vos, J. L. Meinershagen, and T. Bein,Angew. Chem. Int. Ed. Engl., 1996,35, 2211.

    Article  Google Scholar 

  31. D. E. De Vos and T. Bein,J. Organomet. Chem., 1996,520, 195.

    Article  Google Scholar 

  32. D. E. De Vos and T. Bein,J. Chem. Soc., Chem. Commun., 1996, 917.

  33. Y. V. Subba Rao, D. E. De Vos, T. Bein, and P. A. Jacobs,J. Chem. Soc., Chem. Commun., 1997, 355.

  34. C. Zondervan, R. Hage, and B. L. Feringa,J. Chem. Soc., Chem. Commun., 1997, 419.

  35. C. Bolm, D. Kadereit, and M. Valacchi,Synlett, 1997, 687.

  36. B. C. Gilbert, N. W. J. Kamp, J. R. Lindsay-Smith, and J. Oaks,J. Chem. Soc., Perkin Trans. 2, 1997, 2161.

    Google Scholar 

  37. J.-M. Vincent, A. Rabion, V. K. Yachandra, and R. H. Fish,Angew. Chem. Int. Ed. Engl., 1997,36, 2346.

    Article  CAS  Google Scholar 

  38. K. Wieghardt, U. Bossek, B. Nuber, J. Weiss, J. Bonvoisin, M. Corbella, S. E. Vitols, and J. J. Girerd,J. Am. Chem. Soc., 1988,110, 7398.

    Article  CAS  Google Scholar 

  39. J. H. Koek, S. W. Russell, L. van der Wolf, R. Hage, J. B. Warnaar, A. L. Spek, J. Kerschner, and J. DelPizzo,J. Chem. Soc., Dalton Trans., 1996, 353.

  40. G. B. Shul'pin and A. N. Druzhinina,React. Kinet. Catal. Lett., 1992,47, 207.

    Article  Google Scholar 

  41. G. B. Shul'pin and G. V. Nizova,React. Kinet. Catal. Lett., 1992,47, 333.

    Article  Google Scholar 

  42. G. B. Shul'pin, M. C. Guerreiro, and U. Schuchardt,Tetrahedron, 1996,52, 13051.

    Article  Google Scholar 

  43. G. B. Shul'pin, G. V. Nizova, and Yu. N. Kozlov,New J. Chem., 1996,20, 1243.

    Google Scholar 

  44. V. S. Kulikova, O. N. Gritsenko, and A. A. Shteinman,Mendeleev Commun., 1996, 119.

  45. C. Kim, K. Chen, J. Kim, and L. Que, Jr.,J. Am. Chem. Soc., 1997,119, 5964.

    Article  CAS  Google Scholar 

  46. D. H. R. Barton, F. Launay, V. N. Le Gloahec, T. Li, and F. Smith,Tetrahedron Lett., 1997,38, 8491.

    Article  CAS  Google Scholar 

  47. M. Newcomb and P. A. Simakov,Tetrahedron Lett., 1998,39, 965.

    Article  CAS  Google Scholar 

  48. G. B. Shul'pin, D. Attanasio, and L. Suber,J. Catal., 1993,142, 147.

    Article  Google Scholar 

  49. G. V. Nizova, G. Süss-Fink, and G. B. Shul'pin,J. Chem. Soc., Chem. Commun, 1997, 397.

  50. G. V. Nizova, G. Süss-Fink, and G. B. Shul'pin,Tetrahedron, 1997,53, 3603.

    Article  CAS  Google Scholar 

  51. J. H. Baxendale and J. A. Wilson,Trans. Faraday Soc., 1957,53, 344.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 ul. Kosygina, 117977, Moscow, Russian Federation

    G. B. Shul'pin

  2. The University of York, Department of Chemistry, YO1 5DD, York, Heslington, UK

    J. R. Lindsay-Smith

Authors
  1. G. B. Shul'pin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. J. R. Lindsay-Smith
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2459–2466, December, 1998.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Shul'pin, G.B., Lindsay-Smith, J.R. Oxidation with the “H2O2-managanese(IV) complex-carboxylic acid” reagent. Russ Chem Bull 47, 2379–2386 (1998). https://doi.org/10.1007/BF02641538

Download citation

  • Received:

  • Revised:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02641538

Key words

Search

Navigation