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Efficient stereo- and regioselective hydroxylation of alkanes catalysed by a bulky polyoxometalate

Nature Chemistry volume 2, pages 478–483 (2010)Cite this article

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Abstract

Direct functionalization of alkanes by oxidation of C–H bonds to form alcohols under mild conditions is a challenge for synthetic chemistry. Most alkanes contain a large number of C–H bonds that present difficulties for selectivity, and the oxidants employed often result in overoxidation. Here we describe a divanadium-substituted phosphotungstate that catalyses the stereo- and regioselective hydroxylation of alkanes with hydrogen peroxide as the sole oxidant. Both cyclic and acyclic alkanes were oxidized to form alcohols with greater than 96% selectivity. The bulky polyoxometalate framework of the catalyst results in an unusual selectivity that can lead to the oxidation of secondary rather than the weaker tertiary C–H bonds. The catalyst also avoids wasteful decomposition of the stoichiometric oxidant, which can result in the production of hydroxyl radicals and lead to non-selective oxidation and overoxidation of the desired products.

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Figure 1: Structure and reactivity of a divanadium-substituted phosphotungstate catalyst for the selective oxidation of alkanes.

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Acknowledgements

We are grateful to K. Yamaguchi and K. Yonehara for discussions. This work was supported by the Core Research for Revolutional Science and Technology program of the Japan Science and Technology Agency, the Global COE Program Chemistry Innovation through Cooperation of Science and Engineering, the Development in a New Interdisciplinary Field Based on Nanotechnology and Materials Science Programs and a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Science, Sports and Technology of Japan.

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Authors and Affiliations

  1. Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-8656, Tokyo, Japan

    Keigo Kamata, Kazuhiro Yonehara, Yoshinao Nakagawa, Kazuhiro Uehara & Noritaka Mizuno

  2. Core Research for Evolutional Science and Technology, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, 332-0012, Saitama, Japan

    Keigo Kamata, Kazuhiro Uehara & Noritaka Mizuno

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  1. Keigo Kamata
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Contributions

K.K. and N.M. conceived and designed the experiments. K.K., K.Y. and Y.N. carried out the experiments. K.U. analysed the crystallographic data. K.K. and N.M. co-wrote the paper.

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Correspondence to Noritaka Mizuno.

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Kamata, K., Yonehara, K., Nakagawa, Y. et al. Efficient stereo- and regioselective hydroxylation of alkanes catalysed by a bulky polyoxometalate. Nature Chem 2, 478–483 (2010). https://doi.org/10.1038/nchem.648

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