Nickel-Catalyzed Difluoroalkylation of (Hetero)Arylborons with Unactivated 1-Bromo-1,1-difluoroalkanes

A nickel‐catalyzed cross‐coupling between (hetero)arylborons and unactivated 1‐bromo‐1,1‐difluoroalkanes has been developed. The use of two ligands (a bidentate bipyridine‐based ligand, 4,4′‐ditBu‐bpy, and a monodentate pyridine‐based ligand, DMAP) offers a highly efficient nickel‐based catalytic system to prepare difluoroalkylated arenes which have important applications in medicinal chemistry. Ligand combo: The title reaction requires the use of a combined (2+1) ligand system, that is, a combination of a bi‐ and monodentate ligand (4,4′‐ditBu‐bpy + DMAP). This system allows employment of a wide range of unactivated 1‐bromo‐1,1‐difluoroalkanes as coupling partners, thus providing a highly efficient method for applications in drug discovery and development. bpy=bipyridine, DMAP=4‐(N,N‐dimethylamino)pyridine.