Chiral Lithium Amido Zincates for Enantioselective 1,2‐Additions: Auto‐assembling Reagents Involving a Fully Recyclable Ligand

A methodology consisting in carrying out enantioselective nucleophilic 1,2‐additions (ee values up to 97 %) from cheap, easily accessible, and never described before, chiral lithium amido zincates is presented. These multicomponent reactants auto‐assemble when mixing, in a 1:1 ratio, a homoleptic diorganozinc (R2Zn) with a chiral lithium amide (CLA). The latter, obtained after a single reductive amination, plays the role of the chiral inductor and is fully recoverable thanks to a simple acid–base wash, allowing being recycled and re‐use without loss of stereochemical information. Going nucleophilic: This study shows, for the first time, that triorganozincates made of a chiral amido moiety can behave as efficient chemo‐ and enantioselective nucleophiles toward aldehydes. These cheap auto‐assembled reactants incorporate a chiral inductor based on an amine easily recycled thanks to a simple acid–base wash.