Stereoselective Iridium-N,P-Catalyzed Double Hydrogenation of Conjugated Enones to Saturated Alcohols

Asymmetric hydrogenation of prochiral substrates such as ketones and olefins constitutes an important instrument for the construction of stereogenic centers, and a multitude of catalytic systems have been developed for this purpose. However, due to the different nature of the π-system, the hydrogenation of olefins and ketones is normally catalyzed by different metal complexes. Herein, a study on the effect of additives on the Ir-N,P-catalyzed hydrogenation of enones is described. The combination of benzamide and the development of a reactive catalyst unlocked a novel reactivity mode of Crabtree-type complexes toward C═O bond hydrogenation. The role of benzamide is suggested to extend the lifetime of the dihydridic iridium intermediate, which is prone to undergo irreversible trimerization, deactivating the catalyst. This unique reactivity is then coupled with C═C bond hydrogenation for the facile installation of two contiguous stereogenic centers in high yield and stereoselectivity (up to 99% ee, 99/1 d.r.) resulting in a highly stereoselective reduction of enones.