Levulinic acid (LA) is a relatively accessible lignocellulosic platform chemical. It has intriguing functionalities, and it could play a substantial role in the production of bio-based commodities; however, it has thus far failed to gain traction in commercial markets. Here, we describe an approach for aerobic, oxidative cleavage of levulinic acid, which produces maleic anhydride (MA) in good yield. The approach is interesting in that it connects lignocellulose, via levulinic acid, with a robust and relatively high-value commodity market, namely maleic anhydride. Oxidative cleavage occurs here over supported vanadates, and we have to date demonstrated single-pass MA yields as high as 71% of the theoretical maximum at 573K.1 Beyond practical applications, the chemistry described here is intriguing: the general expectation of oxidative ketone cleavage is that it will preferentially break internal bonds of the molecule, yet formation of maleic anhydride (C4) from levulinic acid (C5) requires selective cleavage of the terminal carbon. We demonstrate that monofunctional ketones, such as 2-pentanone, will preferentially cleave at internal positions; thus, this unanticipated selectivity is unique to bifunctional LA. To probe the source of selectivity for methyl cleavage in this system, we additionally consider the oxidative cleavage of several LA and 2-pentanone analogs. 1. Chatzidimitriou, A. and Bond, J.Q., “Oxidation of levulinic acid for the production of maleic anhydride: breathing new life into biochemicals.” Green Chemistry, 17, 8, 4367-4376, 2015.

Aerobic oxidation of levulinic acid over supported vanadates for the production of maleic anhydride

252nd National Meeting (2016)

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