Accessing Illusive E Isomers of α-Ester Hydrazones via Visible-Light-Induced Pd-Catalyzed Heck-Type Alkylation.

A visible-light-induced Pd-catalyzed stereoselective synthesis of alkylated ester hydrazones has been developed. This method operates via generation of a nucleophilic carbon-centered radical from alkyl bromide, iodide, or redox-active ester, followed by its addition to hydrazone, and a subsequent desaturation by palladium. The majority of products have E configuration, which are inaccessible by conventional condensation methods. In addition, a sequential C,N-alkylation protocol has been developed: a reaction between 1,3-dihalides and glyoxylate-derived hydrazone, delivering tetrahydropyridazines.