The selective functionalization of highly complex and biologically active molecules is a powerful technique in which new compounds with potential applications as agrochemicals/pharmaceuticals can be rapidly generated. In addition, this approach can also provide opportunities to interrogate the biological function of the parent molecule. In principle this is a relatively straight forward concept, however in practice, this approach confronts a number of significant challenges, including (a) reagent/reaction compatibility, (b) site- and stereo-selectivity, and (c) opportunities for scale-up. We believe, based on our recent findings, that an opportunity exists to exploit electrosynthetic routes to selective functionalization of these types of complex molecules. Electrosynthesis has been widely studied within the electrochemical community and has great potential for the construction of chemical bonds but represents an underused tool. Recently the area has seen a resurgence of interest from synthetic chemists due to the versatility of applications and the possible green credentials of ''reagentless'' synthesis. Recently we reported the selective hydrocarboxylation of substituted aromatic alkenes utilising electrosynthesis and carbon dioxide. This novel carbon-carbon bond forming process provides unprecedented access to all carbon quaternary centres through the carboxylation of beta,beta-substituted olefins. In a series of preliminary studies, we have also examined the process for the carboxylation of dienes. These promising preliminary findings (& those in Scheme 3) demonstrate the proof-of-principle that selective hydrocarboxylation of a derivative of dehydroalanine (Dha) is possible.