Palladium-Catalyzed Oxy-olefination of Styrenes toward Fluoroallyl Ethers

Allyl ethers are valuable skeletons that occur widely in natural products. They also serve as important synthetic intermediates, particularly as precursors in Tsuji–Trost reactions. However, their fluorinated analogues remain underexplored, despite the good recognition of fluoroalkenes as isosteres of amides in biological chemistry. Herein, we disclosed an expedient Pd-catalytic platform to construct fluoroallyl ethers via oxy-olefination of easily available alkenes with alcohols and 2,2-dibromo-2-fluoroamide compounds involving a CC bond formation process. The protocol demonstrates excellent compatibility with a broad range of aromatic alkenes under mild reaction conditions, including modified biomolecules and drug derivatives containing styrene motifs. Mechanistic investigations suggest that fluoroalkyl radicals and the π-allyl palladium complex play pivotal roles as key intermediates in this transformation.