Organocatalytic Asymmetric Approach to γ,δ-Functionalization of 3-Cyano-4-styrylcoumarins via Bifunctional Catalysis

[Image: see text] A novel organocatalytic reaction cascade between 3-cyano-4-styrylcoumarins and 2-mercaptoacetophenones is described. It is based on stereocontrolled functionalization of cyanocoumarins proceeding in a sequence of thia-Michael/aldol/annulation reactions. This highly diastereo- and enantioselective reaction is realized by employing enantioselective bifunctional catalysis and exhibits a broad substrate scope and excellent functional group tolerance. The synthetic application involves the transformation of the imidoester group, thus opening access to biologically relevant coumarin and δ-lactone-fused products.