Abstract: | In a screening of ligands, ionic liquids and reaction conditions in the Rh‐catalyzed hydrogenation of enamides, a novel multi‐phase reaction system consisting of an ionic liquid (IL) and water (wet ILs) was found to give the most promising results. In many cases such IL/water combinations were superior compared to conventional organic solvents and biphasic ILs/organic co‐solvents media with respect to catalytic performance as well as to catalyst separation and recycling. So far, the best results were obtained with Rh‐ferrocenyl‐diphosphine catalysts (>99% ee). Generally, somewhat lower ees were observed at higher pressure. However, this effect was less pronounced with wet ILs than with conventional solvents. It is shown that IL/water combination allow repeated catalyst recycling without significant loss of activity and that industrially relevant turnover numbers of >10,000 can be obtained. |