A biphasic catalytic system with water-soluble rhodium complexes of sulfonated (R)-2,2 '-bis(diphenylphosphino)-1,1 '-binaphthyl (labeled as (R)-BINAPS) in ionic liquid BMI-BF4 has been developed for the asymmetric hydroformylation of vinyl acetate under mild conditions. The corresponding ruthenium complexes have been investigated for the biphasic asymmetric hydrogenation of dimethyl itaconate. The biphasic asymmetric hydroformylation of vinyl acetate provided 28.2% conversion and 55.2% enantiomeric excess when BMI center dot BF4-toluene was used as the reaction medium at 333 K and 1.0 MPa for 24 h. The biphasic asymmetric hydrogenation of dimethyl itaconate in BMI center dot BF4-' PrOH at 333 K and 2.0 MPa afforded 65% enantiomeric excess with an activity similar to the homogenous analogs. Both biphasic catalytic systems with (R)-BINAPS ligand could be reused several times without significantly decrease in the activity, enantio- and regio-selectivities. The effects of properties of ionic liquid, molar ratio of ligand to rhodium, temperature, pressure and reaction time have been discussed. (C) 2007 Published by Elsevier B.V.