Asymmetric synthesis of (R)-S-(1,2,4-triazol-3-yl)cysteines by nucleophilic addition of triazolethiols to a Ni^IIcomplex with a chiral dehydroalanine Schiff base

An efficient method was developed for the asymmetric synthesis of (R)-S-(1,2,4-triazol-3-yl)cysteines by the addition of 3,4-disubstituted 1,2,4-triazole-5-thiols at the electrophilic C=C bond in a NiII complex of a Schiff base of dehydroalanine with (S)-N-(N-benzylprolyl)aminobenzophenone. The stereoselectivity of the formation of diastereomeric complexes with the (S,R) configuration under conditions of thermodynamic control of the nucleophilic addition exceeds 94%. Acid treatment of the reaction mixtures afforded enantiomerically pure (R)-S-hetarylcysteines (ee >98%).