A paired electrochemical method is presented for the one-pot synthesis of γ,δ-unsaturated α-amino esters. The method involves the in situ generation of organozinc reagents through zinc chloride reduction on the nickel cathode and the TEMPO-mediated oxidation of amino esters on the carbon anode. The presence of an ester moiety in the amine substrate was found to be crucial for achieving high diastereoselectivity.