Selective Dearomatic Deuteration of (Het)arenes via Electrophotocatalysis

Developing green and practical D-labeling techniques is valuable and in high demand for medical chemistry, mechanistic studies, and materials science. Although dearomatic deuteration of simple aromatic systems represents an attractive protocol to access D-labeled compounds, the inherent chemical stability of (het)aromatics leaves successful examples rather scarce. Different from transition metal catalysis, which involves dangerous and expensive deuterium sources, and harsh reaction conditions, represented herein is the first electrophotocatalytic platform for dearomative deuteration of inert (het)arenes. Taking economical D2O as the deuterium source and organic N , N-bis(2,6-diisopro- pylphenyl)perylene-3,4,9,10-bis(dicarboximide) as the electrophotocatalyst, Birch-type deuteration of (het)aromatics is realized with excellent site-selectivity, good functional group compatibility, and highD-incorporation. Late-stage deuteration of complex pharmaceuticals and gram-scale scale-up are easily implemented. This methodology overcomes existing synthetic challenges, and no overreduction reaction occurs. Moreover, the electrophotocatalytic platform works well with renewable solar-to-electricity, offering an effective way to prepare synthetically useful deuterated molecules.