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

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. The ability to selectively transform the C–H bonds of simple alkanes to useful functional groups such as alcohols is a key step in the move away from petrochemical feedstocks. Now, it has been shown that the oxidation of alkanes can be catalysed by a bulky polyoxometalate species using hydrogen peroxide as a stoichiometric oxidant.

Cite this article

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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