Unplugging Asymmetric Synthesis with a Wireless, Self-Pumping Electrochemical Reactor

Herein, we report the first miniaturized, wireless electrochemical flow reactor capable of performing both reactant pumping and asymmetric synthesis within a single, integrated device. The reactor consists of a hollow, conductive polymer tube where the outer polypyrrole (Ppy) shell acts as an electromechanical pump, and the inner layer, constituted of a chiral thiophene-based oligomer, serves as the enantioselective catalyst. This integrated design overcomes mass-transport limitations and eliminates the need for external pumps. By employing an alternating current (AC) protocol, we achieve near-quantitative yield (99%) and exceptional enantioselectivity (>99% ee) for the reduction of acetophenone. The system's utility is showcased across three mechanistically distinct transformations, ketone reduction, sulfide oxidation, and reductive amination, culminating in the direct asymmetric synthesis of Ugi's amine, the chiral probe used in our mechanistic studies, with high stereocontrol (>99.5% ee). This work introduces a new paradigm for reagent-free, pump-free asymmetric synthesis and provides a validated, predictive model for the rational design of smart, automated chemical manufacturing platforms.