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

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Abstract

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

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Acknowledgements

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.

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Authors and Affiliations

  1. Departamento de Química, Universidade Federal de Viçosa, Viçosa, Minas Gerais, 35690-000, Brazil

    Danieli M. Carari & Márcio J. da Silva

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  1. Danieli M. Carari
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  2. Márcio J. da Silva
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Correspondence to Danieli M. Carari.

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Carari, D.M., da Silva, M.J. A Highly Selective Pd(OAc)2/Pyridine/K2CO3 System for Oxidation of Terpenic Alcohols by Dioxygen. Catal Lett 142, 251–258 (2012). https://doi.org/10.1007/s10562-011-0754-4

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  • DOI: https://doi.org/10.1007/s10562-011-0754-4

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