Nickel‐Catalyzed N‐Arylation of Fluoroalkylamines

The Ni-catalyzed N-arylation of b-fluoroalkylamines with broad scope is reported for the first time. Use of the air-stable pre-catalyst (PAd2-DalPhos)Ni(o-tol)Cl allows for reactions to be conducted at room temperature (25 oC, NaOtBu), or by use of a commercially available dual-base system (100 oC, DBU/NaOTf), to circumvent decomposition of the N-(b-fluoroalkyl)aniline product. The mild protocols disclosed herein feature broad (hetero)aryl (pseudo)halide scope (X = Cl, Br, I, and for the first time phenol derived electrophiles), encompassing base sensitive substrates and enantioretentive transformations, in a manner that is unmatched by any previously reported catalyst system.