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.