Abstract
BECAUSE of the chemical inertness of alkanes, the introduction of functional groups into them by oxidation has tended to require severe and thus unselective conditions. The homogeneous and heterogeneous catalysts used for alkene oxidation are ineffective for alkanes1,2. Cleavage of carbon–carbon bonds in the presence of transition metal complexes effects mainly complete oxidation to acids2, although some selectivity is occasionally possible3. Oxyfunctionalization without C–C bond cleavage has also been achieved2,4,5, and high selectivity may be obtained from natural or synthetic metalloporphyrin systems6,7. Here we show that titanium silicalite, a microporous crystalline Ti-silica8, is able to activate secondary and tertiary carbon atoms in alkanes, so that they may be oxidized to alcohols and subsequently to ketones using aqueous H2O2. The catalyst has low regioselectivity for alcohol formation but high reactant selectivity in the formation of ketones.
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Huybrechts, D., Bruycker, L. & Jacobs, P. Oxyfunctionalization of alkanes with hydrogen peroxide on titanium silicalite. Nature 345, 240–242 (1990). https://doi.org/10.1038/345240a0
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DOI: https://doi.org/10.1038/345240a0
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