Synthesis of fluorine-substituted [2.2]paracyclophane-based carbene precursors for copper-catalyzed enantioselective boration of α,β-unsaturated ketones

Fluorine-substituted 2.2]paracyclophane-based carbene precursors have been successfully synthesized and applied to copper-catalyzed asymmetric β-boration of α,β-unsaturated ketones. Fluorination of the planar chiral carbenes has a beneficial impact on the catalytic performance of the relevant complexes. A variety of chiral β-boryl ketones were obtained in excellent yields (up to 99%) and with high enantioselectivities (up to 99% ee).