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 reagents.
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