Enabling Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling of Carbamoyl Fluorides: Mechanism and Scope

The first Ni-catalyzed Suzuki cross-coupling amide synthesis using stable carbamoyl fluoride starting materials under mild conditions is reported. Mechanistic studies are carried out to document the reactivity of nickel toward the CF bond oxidative addition of carbamoyl fluorides and the transmetalation with arylboronic acids. Stoichiometric reactions and isolation of key organometallic intermediates allow us to identify the transmetalation as the most challenging step of the coupling reaction mechanism. The use of tris(4-methoxyphenyl) phosphine ligands enables the development of robust and practical catalytic approach for the synthesis of a broad range of amides.