Photocatalytic Trifluoromethylimination and Sulfonylimination of N -Homoallylsulfonyl Hydrazones with Sulfonyl Chlorides Via Remote 1,4-Imine Migration

A visible-light-mediated trifluoromethylimination and sulfonylimination of N -homoallylsulfonyl hydrazones has been developed via remote 1,4-imine migration using readily available sulfonyl chlorides as radical precursors. In the presence of 4CzIPN and 1,4-dioxane serving as both reaction medium and hydrogen atom transfer reagent, a variety of CF 3 -containing sulfonamide derivatives are efficiently synthesized. Switching the catalytic system to fac -Ir(ppy) 3 /NaOAc in THF enables the analogous sulfonylimination toward structurally diverse β-amino sulfones. A radical cascade pathway featuring alkene radical addition, N–N homolytic cleavage, β-scission-triggered 1,4-imine migration, and a HAT process was proposed.