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

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.