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Closing the radical gap in chemical synthesis

Unstable radical intermediates are harnessed in a microfluidic electrochemical cell Chemists now face the daunting task of identifying synthetic methods that are more practical, scalable, and sustainable. Approaches include the development of safer, more readily available reactants and reagents as well as discoveries in method development that provide more effective and selective synthetic transformations (1, 2). Conventionally, organic synthesis has been conducted through batch processes, but the use of continuous-flow technologies can allow straightforward scale-up, facilitate operational simplicity, and reduce occupational hazards and industrial waste streams (3). On page 1352 of this issue, Mo et al. (4) demonstrate that microfluidic electrochemical technologies can be applied to single-electron transfer (SET) redox-neutral reactions. Their strategy enables the efficient formation and utilization of free-radical intermediates by placing the anode and cathode in close proximity to overcome radical instability. These versatile intermediates were leveraged in Minisci-type reactions of electron-deficient heterocyclic compounds, as well as radical-radical and nickel-catalyzed sp2 carbon–oxygen cross-couplings.