Chemoselective transfer hydrogenation of α,β-unsaturated carbonyl compounds using potassium formate over amine-grafted Ru/AlO(OH) catalysts

Abstract

Grafting of 3-(2-aminoethylamino)propyltrimethoxysilane onto Ru/AlO(OH) resulted in an active and highly chemoselective heterogeneous catalyst for the transfer hydrogenation of α,β-unsaturated carbonyl compounds to the corresponding allylic alcohols. Potassium formate was used as a sustainable hydrogen donor. A range of substrates including cinnamaldehyde, α-amylcinnamaldehyde, citral, 3-methyl-2-butenal, trans-2-pentenal, and trans-hexenal were selectively hydrogenated at the CO moiety with >96% selectivity. In comparison, the unmodified 1 wt% Ru/AlO(OH) catalyzed hydrogenation of cinnamaldehyde at the CC bond, yielding 3-phenylpropanal as the product. Higher loaded samples with 2–10 wt% Ru exhibited 20–25% selectivity to cinnamyl alcohol. The results show that low coordination sites were more selective to hydrogenation of the internal CC than the terminal CO bond. Immobilization of the amine via chemical bonding with hydroxyl groups of the AlO(OH) support blocks adjacent exposed metal sites, increasing the chemoselective reduction of CO. Optimum results were achieved at an amine/Ru ratio of 6. The catalyst maintained high activity and chemoselectivity even after five cycles.