From furfural to fuel: synthesis of furoins by organocatalysis and their hydrodeoxygenation by cascade catalysis.

The synthesis of furoins from biomass-derived furfural and 2-methylfurfural is demonstrated in high yields in green and renewable solvents using N-heterocyclic carbene organocatalysts. The resulting furoin molecules are used as precursors for fuels using cascade catalysis, first by using Pd/C with acidic co-catalysts under very mild conditions to yield oxygenated C12 molecules. Two main products were formed, which we identified as 1,2-bis(5-methyltetrahydrofuran-2-yl)ethane and 1-(5-methyltetrahydrofuran-2-yl)heptanol. The use of a Pd/Zeolite-ß catalyst under more extreme conditions resulted in the complete hydrodeoxygenation of 5,5'-dimethylfuroin to dodecanes in high yields (76%) and exceptional selectivity (94%) for n-dodecane.