Asymmetric Nucleophilic Acylation via Metalated Chiral Amino Cyanides: Enantioselective Synthesis of 3‐Substituted 4‐Oxoesters by Asymmetric Michael Addition

Surprisingly, the synthetic potential of chiral amino cyanides 1 has hardly been exploited. These compounds are readily accessible from a chiral amine and aldehydes in the presence of KCN. After metalation, they serve as chiral acyl anion equivalents and can react, for example, with α,β-unsaturated esters to give oxoesters 2 (ee = 90 to 96%). Up to 91% of the chiral amine can be recovered.