Enantioselective Sequential Catalytic Arylation‐Fukuyama Cross‐coupling of 1,1‐Biszincioalkane Linchpins

Abstract

Abstract1,1‐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(sp3)‐organodimetallics, provides useful methodology to access in a modular fashion acyclic α‐disubstituted ketone products with very high enantiomeric purity.