Addition of carbon centered radicals to methyl 3-(methylamino)acrylate: The regioselectivity of radical addition to enamino esters

► We model by means of DFT the addition of carbon centered radicals to enamino esters. ► Performance of different DFT functionals (hybrid-GGA vs metahybrid-GGAs) was validated against coupled-cluster methodologies. ► According to the computations, enamino esters present a strong ambiphilic character towards radical addition.