Using a flexible synthesis, new chiral iridium N,P complexes with sterically demanding aryl substituents were synthesized and used in the asymmetric hydrogenation of difficult substrates. Unprecedented enantioselectivities were obtained in the asymmetric hydrogenation of a-substituted a,b-unsaturated esters and dihydronaphthalenes. The variety of aryl substituents incorporated into the catalyst has made it possible to obtain useful structure selectivity relationships for important classes of substrates.

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Unprecedented enantioselectivities are obtained in the hydrogenation of α-substituted α,β-unsaturated esters and dihydronaphthalenes. The variety of aryl substituents incorporated into the catalysts makes it possible to provide useful structure selectivity relationships (to be continued). -(WOODMANSEE, D. H.; MUELLER, M.-A.; NEUBURGER, M.; PFALTZ*, A.; Chem.