Catalysis Letters

, Volume 142, Issue 2, pp 251–258 | Cite as

A Highly Selective Pd(OAc)2/Pyridine/K2CO3 System for Oxidation of Terpenic Alcohols by Dioxygen



Molecular sieves, complex organic bases and radical oxidants are commonly used in alcohols oxidation reactions. In this work, we have evaluated the beneficial effects of addition of K2CO3 to Pd(II)-catalyzed oxidation alcohols, which resulted in a remarkable increase in the oxidation reaction rates without selectivity losses. Herein, in a metallic reoxidant-free system, terpenic alcohols (β-citronellol, nerol and geraniol) were selectively converted into respective aldehydes from Pd(II)-catalyzed oxidation reactions in presence of dioxygen. High conversions and selectivities (greater than 90%) were achieved in the presence of the Pd(OAc)2/K2CO3 catalyst and pyridine excess. The exogenous role of others auxiliary anionic and nitrogen compounds was appraised.

Graphical Abstract

Reaction conditions: β-citronellol (2.75 mmol); Pd(OAc)2 (0.05 mmol); pyridine (5.0 mmol); K2CO3 (2.5 mmol); toluene (10 mL); MS3A (0.5 g); O2 (0.10 MPa); 60 °C.

Comparison of systems used in Pd(OAc)2-catayzed oxidation of β-citronellol by dioxygen


Palladium Terpenic alcohol Nitrogen ligand Dioxygen 



The authors are grateful for the financial support from CAPES, CNPq, FAPEMIG and FUNARBE (Brazil). They also wish to thank Prof. Luis Claudio Barbosa for the GC–MS analyses.


  1. 1.
    Muzart J (2003) Tetrahedron 59:5789CrossRefGoogle Scholar
  2. 2.
    Gallezot P (2007) Catal Today 121:76CrossRefGoogle Scholar
  3. 3.
    Pybus DH, Sell CS (2001) The chemistry of fragrances. RSC Paperbacks, CambridgeGoogle Scholar
  4. 4.
    Lenardão EJ, Botteselle GV, Azambuja F, Perin G, Jacob RG (2007) Tetrahedron 63:6671CrossRefGoogle Scholar
  5. 5.
    Yoji H, Takeshi I, Yoshiki O (2002) European Patent EP122516, 2002Google Scholar
  6. 6.
    Brennfhrer A, Neumann H, Beller M (2009) ChemCatChem 1:28CrossRefGoogle Scholar
  7. 7.
    da Silva MJ, Teixeira RR, Carari DM (2009) J Organomet Chem 694:3254CrossRefGoogle Scholar
  8. 8.
    da Silva MJ, de Oliveira AA, da Silva ML (2009) Catal Lett 130:424CrossRefGoogle Scholar
  9. 9.
    da Silva MJ, Gusevskaya EV (2001) J Mol Catal A 176:23CrossRefGoogle Scholar
  10. 10.
    Bäckvall JE, Gogoll AJ (1987) J Chem Soc Chem Commun 1236Google Scholar
  11. 11.
    Peterson KP, Larock RC (1998) J Org Chem 63:3185CrossRefGoogle Scholar
  12. 12.
    Bagdanoff JT, Ferreira EM, Stoltz BM (2003) Org Lett 5:835CrossRefGoogle Scholar
  13. 13.
    Stoltz BM (2004) Chem Lett 33:362CrossRefGoogle Scholar
  14. 14.
    Schultz MJ, Park CC, Sigman MS (2002) Chem Commun 3034Google Scholar
  15. 15.
    Nishimura T, Onoue T, Ohe K, Uemura S (1998) Tetrahedron Lett 39:6011CrossRefGoogle Scholar
  16. 16.
    Nishimura T, Kakiuchi N, Onoue T, Ohe K, Uemura S (2000) J Chem Soc. Perkin Trans 1:1915Google Scholar
  17. 17.
    Nishimura T, Onoue T, Ohe K, Uemura S (1999) J Org Chem 64:6750CrossRefGoogle Scholar
  18. 18.
    Nishimura T, Maeda Y, Kakiuchi N, Uemura S (2000) J Chem Soc. Perkin Trans 1:4301Google Scholar
  19. 19.
    Kumpulainen ETT, Koskinen AMP (2009) Chem Eur J 15:10901CrossRefGoogle Scholar
  20. 20.
    Beccalli EM, Broggini G, Martinelli M, Sottocornola S (2007) Chem Rev 5318Google Scholar
  21. 21.
    Milstein D (2010) Top Catal 53:915CrossRefGoogle Scholar
  22. 22.
    Mandal SK, Jensen DR, Pugsley JS, Sigman MS (2003) J Org Chem 68:4600CrossRefGoogle Scholar
  23. 23.
    Steinhoff BA, Guzei IA, Stahl SS (2004) J Am Chem Soc 126:11268CrossRefGoogle Scholar
  24. 24.
    Gligorich KM, Sigman MS (2009) Chem Commun 3854Google Scholar
  25. 25.
    Cornell CN, Sigman MS (2006) Org Lett 8:4117CrossRefGoogle Scholar
  26. 26.
    Neumann D, Krauss G, Hieke M, Groger D (1983) Plant Med 48:20CrossRefGoogle Scholar
  27. 27.
    Lide DR (ed) (1999) CRC handbook of chemistry and physics, 80th edn. CRC Press, Boca RatonGoogle Scholar
  28. 28.
    Muzart J (2009) J Mol Catal A 308:15CrossRefGoogle Scholar
  29. 29.
    Ringsdoff H, Schlarb B, Venzmer J (1988) Angew Chem Int Ed 27:113CrossRefGoogle Scholar
  30. 30.
    Grushin VV, Alper H (1993) Organometallics 12:1890CrossRefGoogle Scholar
  31. 31.
    Schultz MJ, Hamilton SS, Jensen DR, Sigman MS (2005) J Org Chem 70:3343CrossRefGoogle Scholar
  32. 32.
    Steinhoff BA, King AE, Stahl SS (2006) J Org Chem 71:1861CrossRefGoogle Scholar
  33. 33.
    Nishimura T, Uemura S (2000) Catal Surv Jpn 4:31CrossRefGoogle Scholar
  34. 34.
    Ferreira EM, Stoltz BM (2001) J Am Chem Soc 123:7725CrossRefGoogle Scholar
  35. 35.
    Popp BV, Stahl SS (2007) J Am Chem Soc 129:4410CrossRefGoogle Scholar
  36. 36.
    Popp BV, Stahl SS (2009) Chem Eur J 15:2915CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2011

Authors and Affiliations

  1. 1.Departamento de QuímicaUniversidade Federal de ViçosaViçosaBrazil

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