We recently reported high selectivity toward methyl scission during the catalytic oxidation of the ketone moiety in levulinic acid (4-oxopentanoic acid) over supported vanadium oxides.  This leads to the formation of maleic anhydride in good yields – up to roughly 75% of the theoretical maximum. In contrast, oxidative scission of monofunctional methylketones, such as 2-pentanone, shows poor selectivity toward methyl scission, favoring instead cleavage of internally-positioned C-C bonds. Yields observed during oxidative scission of various linear and branched ketones and keto-acids suggest that a preference for methyl scission is relatively unique to levulinic acid, and that it stems from the bifunctional nature of the molecule.  Here, we attempt to elucidate the key molecular features that lead to high selectivity toward methyl scission and to map the network of reactions leading to maleic anhydride formation during levulinic acid oxidation.  Our discussion is based on consideration of reactivity and selectivity trends as well as spectroscopic analysis.  <br/>

Analysis of selectivity trends during the oxidative scission of ketones and keto-acids

2019 Fall National Meeting

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