Catalytic Asymmetric Synthesis of Chiral Allenylic Fluorides Enabled by Multiple Radical Sorting

Abstract Here, we disclose a nickel‐catalyzed, three‐component asymmetric radical sorting strategy that enables the enantioselective synthesis of axially chiral allenylic fluorides from readily available 1,3‐enynes, fluoroiodomethane, and alkyl bromides. This radical protocol proceeds under mild, reductive conditions, accommodates a broad range of functional groups, including those found in complex bioactive molecules, and demonstrates high chemo‐, regio‐, and enantioselectivity. A previously unrecognized fluorine effect proved essential in dictating both reactivity and stereocontrol in this multicomponent radical coupling. This discovery establishes an efficient protocol for enantioselective multiple radical sorting and provides a modular platform for the catalytic synthesis of fluorine‐containing axial chirality.