Studies on the Synthesis of Perfluoroaryl Sulfides and their Application in Desulfurative Nickel-Catalyzed Reductive Cross-Coupling

The C−S activation and sulfur removal from native thiols is challenging and limits the application of thiols as typical feedstock materials in organic synthesis despite their natural abundance. Herein, we describe a simple procedure to introduce a per-/polyfluoroaryl moiety, which serves as a redox-active scaffold, into alkyl/aryl thiols using nucleophilic aromatic substitution (SNAr) chemistry to activate the C−S bond. The per-/polyfluoroaryl group acts as an electron acceptor in single electron transfer events to generate radical intermediates through cleavage of the C−S bond of mercaptans and utilize them in nickel-catalyzed reductive cross-coupling reactions. In addition, using computational methods, we shed light on the mechanism of this class of SNAr reaction and show that the preference for a concerted or stepwise mechanistic pathway can be easily rationalized through a Marcus-type argument, as well as consideration of the relative stability of the potential energy surfaces.