Successive treatment of (E)-Cα,Cβ-disubstltuted N-enoyl sultams 6 and 13 with organocopper reagents (Me₂CuLi, (CH₂-CH)₂CuLi, Ph₂CuLi in the presence of PBu₃ or SCN⁻) and aq. NH₄Cl gave products 7 and 14, respectivety, with good to excellent stereoface differentiation at Cβ and Cα. Crystallization and mild saponification 7 → 11 and 14 → 15 furnished enantiomerically pure carboxylic acids containing two new stereogenic centers. The postulated reaction topology is supported via acetylatlon of the transient “enolate” (22 → 23) and compared with that of the related organomagnesium- addition/protonation sequence.