This thesis describes the synthesis of several enantiopure hydroxyamides and their subsequent use as chiral ligands in the enantioselective addition of organozinc reagents to carbonyl compounds. Two types of design were used in the synthesis of these hydroxyamide compounds: - C2-symmetrical oxalamides were synthesized from oxalic acid and various chiral aminoalcohols. - C1-symmetrical mandelamides were prepared from (S)-mandelic acid and various amines. These two types of hydroxyamides were used as chiral ligands in different reactions: The oxalamides were used as ligands in the enantioselective addition of diethylzinc to aldehydes. The best results were obtained with ligand L4, derived from oxalic acid and (2S)-1,1,2-triphenylaminoetanol. In the presence of Ti(i-OPr)4, alcohols with the S-configuration are obtained, whereas in the absence of Ti(i-OPr)4, the alcohols are obtained in lower yields and enantioselectivities, with a preference for the R-configuration. The mandelamides were tested in four different enantioselective addition reactions of organozinc reagents to carbonyl compounds: In the enantioselective addition of diethylzinc to aldehydes, the most effective catalyst was a combination of Ti(i-OPr)4 and mandelamide L14, derived from (S)-mandelic acid and (pyridin-2-yl)methanamine, giving the corresponding S-alcohols with ees of up to 88%. In the corresponding addition of dimethylzinc to aldehydes, the best results were obtained by a combination of Ti(i-OPr)4 and mandelamide L11, derived from (S)-mandelic acid and phenylmethanamine. The alcohols were obtained in up to 90% ee. Also in the enantioselective addition of dimethylzinc to -ketoesters, the most effective ligand was mandelamide L11, leading to S--hydroxyesters (ee 90%). In this case, the presence of Ti(i-OPr)4 was not necessary. Finally, the enantioselective addition of alkynylzinc reagents to aldehydes was investigated, with mandelamide L13, derived from (S)-mandelic acid and (S)-1-phenylethanamine, leading to the best results. The resulting alcohols were S, except for heteroaromatic substrates, which had the R-configuration. The presence of Ti(i-OPr)4 was not required, although in order to generate the alkynylzinc reagent it was necessary to heat the mixture of ligand-alkyne-Me2Zn at 70 °C. This reaction was carried out successfully using various terminal alkynes and aldehydes, with especially good results for heteroaromatic aldehydes (yields up to 98%, ee up to 92%).
