Carbohydrate-Functionalized Triazolylidene Iridium Complexes: Hydrogenation Catalysis in Water with Asymmetric Induction.

ABSTRACT

Two sets of carbohydrate-NHC hybrid iridium complexes were synthesised in order to combine properties of carbohydrates and triazolylidene (trz) ligands in organometallic catalysis. One set features a direct trz linkage to the anomeric carbohydrate carbon, while the second set is comprised of an ethyl linker between the two functional units. Deprotection of the carbohydrate afforded hybrid complexes that efficiently catalyse the direct hydrogenation of ketones in water. The catalytic activity of the hybrid complexes was influenced by the pH of the aqueous medium and surpassed the activity of carbohydrate-free or acetyl-protected analogues (>90 % vs 13 % yield). While no enantiomeric induction was observed for the ethyl-linked hybrids, a moderate enantiomeric excess (ee) was induced by the directly linked systems. Moreover, these carbohydrate-trz hybrid complexes displayed mixed inhibitory activity towards a glycosidase from H. orenii that contain a glucose binding site.