Hydroformylation of vinyl arenes (p-metboxystyrene and p-fluorostyrene) was performed in aqueous solutions using as catalyst precursor Rh(mu-OMe)(cod) (cod = 1,5-cyclooctadiene) associated with the sulfonated 1,3-diarylphosphines (tetra-sulfonated 1,3-bis(diphenylphosphino)propane (dpppts)) and the chiral (S,S)-bdppts (2,4-bis(diphenylphosphino)pentane). The influence of pH on the reaction rate was studied. After 24 h conversion was practically total with the achiral system in basic medium for the substituted styrene substrates. Selectivities in aldehydes were >85%. At neutral pH, the asymmetric hydroforrnylation of p-substituted styrenes using the rhodium-bdppts systems provides low conversion but the enantioselectivities were as high as 66%, the highest reported so far for this kind of substrates in aqueous systems. Comparison experiments using rhodium precursors with the non-sulfonated bdpp in organic solvents indicated that the enantioselectivity was higher in aqueous solutions for the p-methoxystyrene derivative and slightly lower for p-fluorostyrene. However, in both the cases the conversions in aqueous systems were low. High-pressure NMR and IR experiments in water/methanol indicate that [RhH(CO)(2)(sulfonated diphosphine)] species form under catalytic conditions in basic medium. At neutral pH, the main species observed in the case of the bdppts ligand is Rh(bdppts)(2) which may account for the low conversion in this medium. (C) 2002 Elsevier Science B.V. All rights reserved.