Homolytic N−S Bond Cleavage in Vinyl Triflimides Enabled by Triplet–Triplet Energy Transfer. Issue 53 (8th August 2022)

• Record Type: Journal Article
• Authors: Strauch, Christina; Schroeder, Sebastian; Grelier, Gwendal; Niggemann, Meike
• Is Part Of: Chemistry. Volume 28:Issue 53(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-08-08
• Subjects: homolytic cleavage -- photochemistry -- sulfonamides -- trifluoromethylation -- triplet–triplet energy transfer; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202201830
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: 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 CF3 reagents. Abstract : No need to pay for extras : Vinyl triflimides are a new compound class with unknown reactivity. Computational analysis identified homolytic cleavage of the N−Tf bond induced by triplet–triplet energy transfer (EnT) as an accessible reaction manifold. This hypothesis was verified, and vinyl triflimides were transformed into a range of α‐quaternary, β‐trifluoromethylated amines in a 1, 2‐difunctionalization reaction with no need for external CF3 reagents.