Novel 2,3:4,6-di-O-isopropylidene-alpha-D-glucopyranosyl-(1,1)-4,6-O-isopropylidene-2,3-di-O-diphenylphosphino-alpha-D-glucopyranoside (2), 2,3:4,6-di-O-cyclohexylidene-alpha-D-glucopyranosyl-(1,1)-4,6-O-cyclohexylidene-2,3-di-O-diphenylphosphino-alpha-D-glucopyranoside (4), and 2,3:4,6-di-O-cyclohexylidene-beta-D-glucopyranosyl-(1,1)-4,6-O-cyclohexylidene-2,3-di-O-diphenylphosphino-beta-D-glucopyranoside (11) were prepared from the corresponding alpha,alpha- or beta,beta-trehalose. The ligands were transformed into cationic Rh complexes, such as [Rh(alpha-D-glucopyranosyl-(1,1)-2,3-di-O-diphenylphosphino-alpha-D-glucopyranoside)(cod)]BF(4) (3) and [Rh(beta-D-glucopyranosyl-(1,1)-2,3-di-O-diphenylphosphino-beta-D-glucopyranoside)(cod)]BF(4) (12) bearing free hydroxy groups. These complexes were soluble in water and were efficient catalysts for the asymmetric hydrogenation of dehydroamino acids and their esters in water or an aqueous/organic biphasic medium with high enantioselectivity (up to 99.9% ee). Aqueous biphasic systems offer an easy separation of the aqueous catalyst phase from the product phase and allow recycling of the catalyst phase without the loss of enantioselectivity.