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New chiral sulfides and disulfides were synthesized from readily available and inexpensive cysteine by straightforward methods in order to elucidate the relative importance of the various donor atoms (N, O, S) available in free or alkylated form resulting in covalent or dative bonds to the metal, respectively. Their application in the addition of diethylzinc to aldehydes provides secondary alcohols with up to 99% ee, and S-configuration, when catalytic amounts of disulfide ligands with the ability to form an S-Zn bond were used. In contrast to this, benzyl alcohols with the opposite absolute configuration R could be achieved, albeit with decreased yield and enantioselectivity, by the use of alkylated sulfide ligands.