Shuttle Hydrogen Atom Transfer for Hydro-Fluorosulfonylation of Haloalkynes without β-Scission

Radical addition to haloalkynes often produces alkynylation products with the cleavage of these halogen groups. Herein, we report a direct hydrogen atom transfer (<i>d</i>-HAT) photocatalysis-enabled shuttle HAT system that realizes hydro-fluorosulfonylation of alkynyl bromides and chlorides without β-scission. Our regio- and stereoselective hydro-fluorosulfonylation strategy enables facile access to α-halo sulfonyl fluorides, which are challenging to synthesize with previous methods. The retention of these bromo and chloro substituents enables versatile downstream transformations.