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.