Synthesis of Tetrasubstituted Alkenes by Rhodium-Catalyzed Regioselective Cyano Transfer

We describe herein a novel, general, and robust approach to structurally diversified alkenyl nitriles through a Rh-catalyzed cyano transfer reaction between alkynyl-malononitrile derivatives and aryl/alkenyl boronic acids. This reaction exhibits high chemo- and regioselectivity and a broad substrate scope. The tetrasubstituted alkenyl dinitriles (34 examples, average 58% yield) are obtained through substrate tuning and ligand control.