Electrochemical transformations involve complex parameter interactions, ranging from universal chemistry variables such as solvent and reagents to specialist factors including electrode material and current density. Hence, the development of a robust and scale-independent electrochemical reaction can currently be a challenge. High-throughput experimentation (HTE) is an enabling method for reaction optimization and robustness testing. Here we provide an industrial and academic perspective on the state of the art of the combination of HTE with electrochemical reaction optimization for applications, including scale-up. We then present our vision for a future in which HTE reduces barriers to wide adoption of electrochemistry across the field of chemical synthesis.

A mechanistic study on use of alternating potential (i. e. electrode polarity switching) in synthetic organic electrochemical method development using the IKA ElectraSyn 2.0 is described. Unexpected product selectivity challenges revealed that alternating potential facilitated direct, rather than mediated, electrochemical benzylic C−H oxidation of toluene derivatives. Whilst constant potential irrespective of the direction of electrode polarity was expected, our in‐depth analysis revealed changes in the magnitude of applied potential with periodic switching of electrode polarity. These findings highlight an equipment engineering concern that is likely to influence and inform optimization strategies for a wide range of synthetic organic electrochemical methods under development.

An electrochemical method for the green and practical synthesis of a broad range of substituted isoxazoline cores is presented. Both aryl and more challenging alkyl aldoximes are converted to the desired isoxazoline in an electrochemically enabled regio‐ and diastereoselective reaction with electron‐deficient alkenes. Additionally, in‐situ reaction monitoring methods compatible with electrochemistry equipment have been developed in order to probe the reaction pathway. Supporting analyses from kinetic (time‐course) modelling and density functional theory support a stepwise, radical‐mediated mechanism, and discounts hypothesised involvement of closed shell [3+2] cycloaddition pathways.