Selective Dearomatic Deuteration of (Het)arenes via Electrophoto-catalysis

Selective dearomatic deuteration of simple aromatic systems, the most abundant and important building blocks across molecular sciences, represents an attractive protocol to access D-labeled compounds. Nevertheless, due to the inherent chemical stability of (het)aromatics, successful examples remain scarce and typically rely on transition metals, dangerous and expensive deuterium sources, and harsh reaction conditions. Herein, a mild and green electrophotocatlytic platform for dearomative deuteration of inert (het)arenes is reported for the first time. Taking economical D2O as deuterium source and N,N-bis(2,6-diisopropylphenyl)perylene-3,4,9,10-bis(dicarboximide) as electrophotocatalyst, the Birch-type deuteration of (het)aromatics is realized through direct single electron transfer with excellent site-selectivity, high D-incorporation and good functional group compatibility. Remarkably, no overreduction reaction occurs. Late-stage deuteration of complex pharmaceuticals and gram-scale scale-up are easily implemented. Moreover, the electrophotocatlytic platform works well with renewable solar-electricity.