Zinc Carbenoid-mediated Chain Extension: Preparation of α,β-Unsaturated-γ-Keto Esters and Amides

An efficient one-pot preparation of α,β-unsaturated-γ-keto esters and amides has been developed. A zinc carbenoid-mediated chain extension of a β-dicarbonyl substrate provides access to an intermediate zinc enolate, which is treated sequentially with a halogen and amine base. This method has been applied to a variety of ester and amide starting materials, as well as to amino acid-derived substrates and to a formal synthesis of (R,R)-(−)-pyrenophorin