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Palladium-Catalysed Oxidation of Bicycle Monoterpenes by Hydrogen Peroxide in Acetonitrile Solutions: A Metal Reoxidant-Free and Environmentally Benign Oxidative Process

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Abstract

Currently, the oxidative transformations of natural olefins are complicated for competitive reactions such as isomerization, skeletal rearrangements and nucleophilic addition. These concurrent reactions are promoted by metal reoxidant, normally a Lewis acid, and by protic solvent. In this article, the oxidation of terpenes, namely camphene, β-pinene, α-pinene and 3-carene were performed in PdCl2/H2O2/CH3CN system. This metal reoxidant-free system showed highly efficient, especially on camphene and β-pinene oxidation, which resulted in the selective conversion of these substrates into epoxy-derivates and allylic oxidation products, respectively. Additionally, the effects of the principal reactional parameters such as the peroxide/catalyst and substrate/catalyst molar ratio were also investigated.

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Acknowledgments

Grateful for the financial support from CNPq, FAPEMIG and FUNARBE (Brazil). The authors wish to thank Prof. Sergio Antonio Fernandes and the MS student Lucas Micqueias Arantes for their help in NMR analysis, in addition to Prof. Luis Claudio Barbosa for GC–MS analyses.

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Authors and Affiliations

  1. Chemistry Department, Federal University of Viçosa, Viçosa, Minas Gerais, 36570-000, Brazil

    Alexandre Almeida de Oliveira, Milene Lopes da Silva & Márcio José da Silva

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  1. Alexandre Almeida de Oliveira
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  2. Milene Lopes da Silva
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  3. Márcio José da Silva
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Correspondence to Márcio José da Silva.

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de Oliveira, A.A., da Silva, M.L. & da Silva, M.J. Palladium-Catalysed Oxidation of Bicycle Monoterpenes by Hydrogen Peroxide in Acetonitrile Solutions: A Metal Reoxidant-Free and Environmentally Benign Oxidative Process. Catal Lett 130, 424–431 (2009). https://doi.org/10.1007/s10562-009-9970-6

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  • DOI: https://doi.org/10.1007/s10562-009-9970-6

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