Two obstacles needed to be overcome to realize the vision set forth above (Figure ). First, an expansion of the initial dDCC scope to encompass substrates containing an α-heteroatom functionality was necessary. As a model system for this challenge, the coupling of proline derivative 8 and glycine derivative 9 was studied. First generation dDCC conditions afforded only 8% of the desired coupling product 10 along with a variety of decarboxylated products such as the corresponding pyrrolidine, dihydropyrrole, and proline dimer (see SI for details). These byproducts were indicative of substantial redox-active ester (RAE) reduction without productive coupling, a situation encountered previously in electrochemical decarboxylative vinylation and arylation studies. In that work, the key breakthrough involved the use of an in-situ generated Agnanoparticle deposited cathode, which primarily modulates multiple reduction events (e.g. concomitant reduction of Ni as well as RAE) on the cathode to improve the chance of successful coupling. Accordingly, this approach was tested for the dDCC coupling of 8 and 9. Indeed, by simply adding sub-stoichiometric amounts of Ag salt in addition to changing solvent (from DMF to NMP) and sacrificial anode material (from Zn to Mg), the yield of 10 was dramatically improved from 8% to 67% (see SI for more details on reaction optimization). The optimal ligand for this coupling was found to be tridentate ligands L1 and L2, the same type of ligands used in the previous dDCC study.