Desulfurative Deuteration of (Hetero)Aryl Sulfides With D ₂ O by Nickel Catalysis

Selective deuteration of (hetero)aryl rings is of great significance and interest, yet it has remained a challenge, especially when employing D 2 O as deuterium source. Herein, the selective desulfurative deuteration of widely available (hetero)aryl sulfides with D 2 O (mostly 1.5 or 3.0 equiv.) has been established by nickel catalysis. This strategy affords an efficient and robust route for the synthesis of a wide range of deuterated (hetero)arenes (87 examples, > 10 different heterocycles) in generally good yields and high deuterium incorporation with good functional group compatibility. The catalytic reaction could be applied to scaled‐up synthesis (e.g., 6.4 g for product 2 , 0.1 mol% Ni catalyst, 590 TON) and late‐stage deuteration of various drugs and bioactive molecules.