An insoluble chiral polymer-supported rhodium complex closely related to the soluble Rh(I)-diop complex (diop = 2,3-0-isopropylidene-2,3-dihydroxy-l,4-bis(diphenylphosphino)butane ( 1)) was prepared using a Merrifield resin. This insoluble system (suspended in benzene) catalyzes the asymmetric hydrogenation of aethylstyrene and methyl atrópate with a much lower efficiency than in solution, and ethanol inhibits the catalysis. In contrast, both catalytic systems, soluble and insoluble, are very efficient for asymmetric hydrosilylation of ketones (acetophenone, methyl benzyl ketone, isobutyrophenone). For a given ketone, the optical yield strongly depends upon the silane used. Dihydrosilanes (diphenylsilane, phenylmethylsilane, -naphthylphenylsilane) are always better than monohydrosilanes (triethylsilane, triethoxysilane, triphenylsilane). Optical yields up to 58 % were obtained. In all cases, the insoluble catalyst can be filtered and easily reused. ne of the most recent and important advances in asymmetric synthesis is the use of a soluble chiral catalyst. Soluble catalysts can be better defined than the heterogeneous ones, and in such complexes it is often easy to vary widely the steric and electronic environment of the catalytically active site in order to optimize both the chemical and optical yields of an asymmetric synthesis.The best results have been obtained in oligomerization of olefins with nickel catalysts2 3456or in reduction with a rhodium catalyst1•3-6 or cobalt complexes.7 8Optical yields as high as 70-90 % have been observed.However, in the use of a soluble catalyst, a problem of practical importance is encountered: the separation of the catalyst from the reaction products requires special treatment which usually destroy it. One way to solve this problem would be to fix the catalyst on a solid support in a way that retains the advantages observed in solution. Recently some authors described the introduction of phosphine groups into polystyrene. This phosphinated resin has been used as a ligand in rhodium or platinum complexes in order to catalyze the hydrogenation,8-10 hydrosilylation,9 10and hydroformyla-tion11 of olefins. In all cases, the insoluble catalyst (1) Part I: .