Homolytic N−S Bond Cleavage in Vinyl Triflimides Enabled by Triplet–Triplet Energy Transfer

Vinyl triflimides are a new compound class with unknown reactivity. A computational analysis identified homolytic cleavage of the N−Tf bond induced by triplet–triplet energy transfer (EnT) as a highly interesting reaction type that might be accessible. A combination of experimental and mechanistic work verified this hypothesis and proved the generated radicals to be amenable to radical–radical coupling. Thereby, vinyl triflimides were transformed into a range of α‐quaternary, β‐trifluoromethylated amines in a 1,2‐difunctionalization reaction with no need for external CF(3) reagents.