Biomimetic asymmetric hydrogenation

Enzymes and synthetic organometallic catalysts utilize different approaches for the creation of chiral centers in prochiral substrates. While chiral organometallic catalysts realize the transfer of chirality mainly by repulsive interactions, several enzymes use preferentially stereodiscriminating hydrogen bonding. To investigate if hydrogen bonding within the catalyst-substrate assembly can also have a benefit on the rhodium diphosphine-catalyzed asymmetric hydrogenation, some model metal complexes and substrates were investigated. As 'biomimetically acting' functionalities, hydroxy groups were incorporated in the chiral ligand. Three secondary interactions could be identified by different analytical methods which influence rate and enantioselectivity of the catalytic reaction: 1) HO/Rh-interactions, 2) HO/HO-interactions within the backbone of the ligand, and 3) hydrogen bonding between HO-groups of the ligand and functional groups of an appropriate substrate. Due to the effect of the additional hydroxy groups, enantioselectivities by up to 99% ee could be induced in the hydrogenation product even with water as solvent. (C) 2001 Wiley-Liss, Inc.