Stereodivergent Palladium-Catalyzed C-F Bond Functionalization of gem-Difluoroalkenes.

We herein describe a stereodivergent C-F bond functionalization of gem-difluoroalkenes. Using trisubstituted β,β-difluoroacrylates, both E and Z monofluoroalkene products can be obtained with excellent diastereoselectivities. The design of two different reaction manifolds, i.e., Pd(II)- versus Pd(0)-catalyzed cross-coupling of boronic acids, is the key to stereocontrol.