Copper/Photoredox Dual‐Catalyzed Stereodivergent Hydrofluoroalkylation of Terminal Alkynes ^†

Comprehensive Summary Allylic alcohols serve as highly versatile building blocks in organic synthesis. Despite their utility, catalytic methods for accessing fluoroalkyl allylic alcohols from simple alkynes remain scarce, particularly those enabling stereodivergent synthesis. Herein, we report a copper/photoredox dual‐catalyzed hydrofluoroalkylation reaction of terminal alkynes with bromofluoroethanol benzoate reagent. This protocol provides stereodivergent access to ( E )‐ and ( Z )‐fluoromethyl allylic alcohol derivatives in moderate to good yields. The transformation exhibits broad substrate scope and functional group tolerance, proceeds under mild conditions, and employs a readily available fluoromethyl synthon. Mechanistic studies reveal a radical pathway featuring aminoalkyl radical‐mediated halogen‐atom transfer (XAT), copper‐assisted ketyl radical addition to the alkyne, and triplet energy transfer (EnT)‐promoted double‐bond isomerization as the key steps.