text: Alkenes that are particularly amenable to asymmetric hydrogenation often feature a polar functional group adjacent to the site to be hydrogenated.  In the absence of this functional group, catalysis often results in low ees.  For some unfunctionalized olefins, iridium with P,N'-based ligands) have proven effective, however. Alkene substrates are often classified according to their substituents, e.g., 1,1-disubstituted, 1,2-diaryl trisubstituted, 1,1,2-trialkyl and tetrasubstituted olefins. and even within these classes variations may exist that make different solutions optimal.
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  Conversely to the case of olefins, asymmetric hydrogenation of enamines has favoured diphosphine-type ligands; excellent results have been achieved with both iridium- and rhodium-based systems. However, even the best systems often suffer from low ee's and a lack of generality. Certain pyrrolidine-derived enamines of aromatic ketones are amenable to asymmetrically hydrogenation with cationic rhodium(I) phosphonite systems, and I and acetic acid system with ee values usually above 90% and potentially as high as 99.9%. A similar system using iridium(I) and a very closely related phosphoramidite ligand is effective for the asymmetric hydrogenation of pyrrolidine-type enamines where the double bond was inside the ring: in other words, of dihydropyrroles. In both cases, the enantioselectivity dropped substantially when the ring size was increased from five to six.