1,1‐Bis(iodozincio)alkanes are used as dinucleophilic linchpins in an enantioselective double cross‐coupling reaction sequence involving aryl iodides and then thioesters. The two catalytic C−C bond‐forming reactions are achieved in the same pot through two distinct palladium‐based catalytic systems: a first non‐enantioselective one delivering configurationally labile secondary benzylzinc species from an achiral precursor, and a second enantioconvergent one that operates a highly efficient dynamic kinetic resolution of the racemic intermediates. This strategy, new in the area of asymmetric synthesis through two consecutive electrophilic substitution reactions of geminated C(sp 3 )‐organodimetallics, provides useful methodology to access in a modular fashion acyclic α ‐disubstituted ketone products with very high enantiomeric purity.