A diastereodivergent asymmetric desymmetrization of azetidinium salts with benzothiazoleamides as carbon nucleophiles through a chiral N,N'-dioxide/Mg(II) complex-promoted ring-opening reaction is realized by tuning ligands. Both syn- and anti-chiral δ-amino acid derivatives bearing benzothiazole structure were obtained in moderate to good yields and dr and ee values. DFT calculations indicated that the diastereodivergency stems from the different size of the chiral pocket formed by variable substructures of the ligands, leading to the opposite attack direction of the nucleophiles.