Scalable and Selective Electrochemical Hydrogenation of Polycyclic Arenes

The reduction of aromatic compounds constitutes a fundamental and ongoing area of investigation. The selective reduction of polycyclic aromatic compounds to give either fully or partially reduced products remains a challenge, especially in applications to complex molecules at scale. Herein, we present a selective electrochemical hydrogenation of polycyclic arenes conducted under mild conditions. A noteworthy achievement of this approach is the ability to finely control both the complete and partial reduction of specific aromatic rings within polycyclic arenes by judiciously varying the reaction solvents. Mechanistic investigations elucidate the pivotal role played by in situ proton generation and interface regulation in governing reaction selectivity. The reductive electrochemical conditions show a very high level of functional-group tolerance. Furthermore, this methodology represents an easily scalable reduction (demonstrated by the reduction of 1 kg scale starting material) using electrochemical flow chemistry to give key intermediates for the synthesis of specific drugs. An electrochemical approach for the selective hydrogenation of aromatic hydrocarbons has been proposed. Detailed mechanistic studies indicate that the selectivity is attributed to combined effects of in situ released protons during anodic oxidation and significant differences in H+ mobility among various solvents. image