This account brings together the recent experimental and computational data on the mechanism of Rh-catalyzed asymmetric hydrogenation of activated double bonds. Two alternative reaction pathways (unsaturated and dihydride) are compared. It is suggested that the differences in these mechanisms are not primarily important for stereoselection, since they join in a single pathway before stereoselection occurs. This approach was used to rationalize the present discrepancies in the prediction of the sense of enantioselection for the P-stereogenic ligands and the ligands with backbone chirality.
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