Fluoride‐Transfer Asymmetric Allylic Alkylation Enables Regiodivergent, Stereoselective Cross‐Electrophile Coupling

Asymmetric allylic alkylation (AAA) is a widely used strategy for stereoselective formation of C─C bonds. Yet, conventional methods often exhibit poor atom economy as the leaving group is generally wasted. Herein, we report a fluoride-transfer asymmetric allylic alkylation (AAA) in which all the atoms of the reagents are incorporated into the final products. The catalytic platform enables regiodivergent, stereoselective cross-electrophile coupling of allyl fluorides and gem-difluoroalkenes, where the regiochemical outcome is directed by the selective catalytic activation of one or the other electrophilic partner. The resulting atom-efficient AAA protocol provides a regiocontrollable access to homoallylic trifluoromethylated compounds from a common set of electrophilic starting materials.