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The α-alkylation of β-heterosubstituted carbonyl compounds leads to a surprising result in the case of L-(+)-N-formylaspartic acid di-tert-butyl ester: A mixture of the β- and α-substituted aspartic acid derivatives (1) and (2) (ca. 7:2) is obtained. The erythro-isomers of (1) are formed stereospecifically, while, interestingly, an enantiomer of (2) is formed in excess; R[DOUBLE BOND]CH3, C2H5, CH2CH[DOUBLE BOND]CH2, CH2C6H5.