Biphasic asymmetric hydroformylation and hydrogenation by water-soluble rhodium and ruthenium complexes of sulfonated (R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl in ionic liquids

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·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·BF4–iPrOH 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.

Graphical abstractBiphasic catalytic systems with water-soluble rhodium and ruthenium complexes of sulfonated (R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl ((R)-BINAPS) in ionic liquid have been developed for the asymmetric hydroformylation and hydrogenation under mild conditions. The biphasic catalytic systems with (R)-BINAPS ligand could be reused several times without significantly reducing the activity, enantio- and regio-selectivities.Figure optionsDownload full-size imageDownload as PowerPoint slide