A nickel-catalyzed cross-coupling of gem-difluorinated cyclopropanes with boronic acids was reported, providing the corresponding arylated 2-fluoroallylic scaffolds with high regioselectivity and Z-stereoselectivity. Mechanistic studies proposed a Ni(II)-fluoroallyl pathway and clarified the origin of the high linear selectivity.

Comprehensive Summary

Herein, we report nickel-catalyzed cross-coupling of gem-difluorinated cyclopropanes with boronic acids, providing the corresponding arylated 2-fluoroallylic scaffolds. This approach used commercially available phosphine ligand Xantphos to obtain monofluorinated alkenes with high regioselectivity and Z-stereoselectivity. Mechanistic studies proposed a Ni(II)-fluoroallyl pathway and excluded the radical pathway. Meanwhile, DFT study of the reductive elimination clarified the origin of the high linear selectivity.