Hydrogenation of levoglucosenone to renewable chemicalsElectronic supplementary information (ESI) available: Gaussian DFT calculations; 13C NMR of reaction products; CO chemisorption data; synthesis of reaction intermediates; product deconvolution methods; solvent degradation data; and catalyst recycling data. See DOI: 10.1039/c6gc03028a

We have studied the hydrogenation of levoglucosenone (LGO) to dihydrolevoglucosenone (Cyrene), levoglucosanol (Lgol), and tetrahydrofurandimethanol (THFDM) and elucidated the reaction network over supported palladium catalysts. At low temperature (40 ° C) over a Pd/Al 2 O 3 catalyst, LGO is selectively hydrogenated to Cyrene. At intermediate temperatures (100 ° C) over a Pd/Al 2 O 3 catalyst, Cyrene is selectively hydrogenated to Lgol, with an excess of the exo -Lgol isomer produced over the endo -Lgol isomer. At higher temperatures (150 ° C) over a bifunctional Pd/SiO 2 -Al 2 O 3 catalyst, Lgol is converted to THFDM in 58% selectivity, with 78% overall selectivity to 1,6-hexanediol precursors. The ratio of cis -THFDM relative to trans -THFDM is approximately 2.5, and this ratio is independent of the Lgol feed stereoisomer ratio. Tetrahydropyran-2-methanol-5-ketone (THP2M5one) and tetrahydropyran-2-methanol-5-hydroxyl (THP2M5H) are side-products of Lgol hydrogenolysis, but neither of these species are precursors to THFDM. Herein, we elucidate the reaction network for catalytic hydrogenation of the biomass-derived intermediate levoglucosenone into several different renewable chemicals.