Palladium-Catalyzed Asymmetric Allylic Fluoroalkylation/Trifluoromethylation.

The first palladium-catalyzed asymmetric allylic trifluoromethylation is disclosed. The methodology evokes a fundamental principle by which the synergistic interplay of a leaving group and its subsequent activation of the nucleophilic trifluoromethyl group enabled the reaction. Allyl fluorides have been shown to be superior precursors for generation of π-allyl complexes, which lead to trifluoromethylated products with high selectivities and functional group tolerance. This study highlights the unique role of a bidentate diamidophosphite ligand class in palladium-catalyzed reactions that allow a challenging transformation to proceed.