Nickel‐Catalyzed Hydro‐ and Deutero‐dehalogenations of (Hetero)Aryl Halides under Aqueous Micellar Catalysis Conditions

Efficient Ni-catalyzed hydrodehalogenations and deuterodehalogenations of aryl/heteroaryl halides are reported herein. This new technology can be used to incorporate not only hydrogen, but also deuterium into various aromatic/heteroaromatic compounds with high efficiency, using 2-6 mol % nickel in the presence of stoichiometric NaBH₄. Over 40 examples have been successfully converted to the corresponding (hetero)arenes in excellent yields. The process is conducted under green chemistry conditions: in water enabled by designer surfactants, a medium which can be readily recycled. Minimal organic solvent, needed given the small (academic) scale of the reactions, is used for product isolation, resulting in low E-Factors. Additionally, sterically hindered substrates are amenable, as are selected APIs that feature carbon-fluorine bonds.