Hydrostannylation-Cross-Coupling Strategy for the Stereoselective Synthesis of Alkylidenemalonates and Related α,β-Unsaturated Esters

Abstract

A method for the stereoselective synthesis of alkylidenemalonates and related α, β-unsaturated esters by a hydrostannylation–cross-coupling process has been developed. Pd-catalyzed and radical hydrostannylation of propiolate derivatives stereoselectively provided α-alkoxycarbonyl (E)- and (Z)-vinylstannanes, respectively, which were then converted into alkylidenemalonates by the Stille coupling reaction. A one-pot process was also realizable for the Pd-catalyzed reactions.