Metal-catalyzed reductive deamination of glutamic acid to bio-based dimethyl glutarate and methylamines

Glutamic acid is a promising renewable platform molecule which is abundantly available in biomass waste streams; it is also efficiently manufactured by fermentation. Here we report the reductive deamination of glutamic acid to bio-based dimethyl glutarate and methylamines. In order to recycle nitrog...

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Veröffentlicht in:Green Chemistry 2017-02, Vol.19 (8), p.1866-1876
Hauptverfasser: De Schouwer, Free, Cuypers, Thomas, Claes, Laurens, De Vos, Dirk
Format: Artikel
Sprache:eng
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Zusammenfassung:Glutamic acid is a promising renewable platform molecule which is abundantly available in biomass waste streams; it is also efficiently manufactured by fermentation. Here we report the reductive deamination of glutamic acid to bio-based dimethyl glutarate and methylamines. In order to recycle nitrogen in an industrially relevant co-product, glutamic acid was modified to N,N-dimethylglutamic acid by a mild reductive alkylation with Pd/C. Subsequently, selective C-N hydrogenolysis in methanol resulted in dimethyl glutarate and trimethylamine. A wide screening of transition metals (Pt, Pd, Rh and Ru) immobilized on various supports showed that the highest yields of dimethyl glutarate were obtained with Pt/TiO2. An FTIR study and kinetic experiments on metal-loaded and unloaded supports demonstrate that the interplay between the metal and the moderate acidity of the support results in the excellent C-N hydrogenolysis activity and selectivity. Finally, reaction parameter optimization resulted in 81% yield of dimethyl glutarate with 1 wt% Pt/TiO2 at 225 °C, 30 bar H2 after 8 h.
ISSN:1463-9262