Nickel-Catalyzed Monofluoroalkylation of Arylsilanes via Hiyama Cross-Coupling.

The first example of nickel-catalyzed monofluoroalkylation of arylsilanes has been developed with readily available fluoroalkyl halides. This novel transformation has demonstrated high reactivity, broad substrate scope, excellent functional group tolerance, and mild reaction conditions. The selective activation of a relatively inert C-Si bond for slow release of aryl carbanion is the key reason for reducing the amount of arylmetal species, which makes this method more promising for fluorine-containing modification of complex bioactive molecules. Mechanistic investigations indicate that a free fluoroalkyl radical is involved in this catalytic cycle.