Work

Protodefluorinated Selectfluor® heteroaggregate photoinduces direct C (sp3)–H fluorinations without photocatalyst

Year: 2025

Type: article

Abstract: Herein, we uncover a hitherto hidden role of H-TEDA(BF4)2 - a cheap, stable, recoverable by-product of radical C(sp 3)-H fluorinations using Selectfluor®. This forms a photoactive, mixed heteroaggregate with Selectfluor® which underlies the reactivity of visible light photochemical fluorination reactions of unactivated C(sp 3)-H bonds. Where previous reports claim to be ‘photocatalytic’, reactions work without photocatalyst when H-TEDA(BF4)2 is dosed in at the start. Our results demonstrate that ‘photocatalysts’ are only necessary to generate a sufficient amount of nascent H-TEDA(BF4)2, whose heteroaggregate with Selectfluor® takes over as the main photoactive species. Mechanistic studies suggest the formation of a heteroaggregate between H-TEDA(BF4)2 and Selectfluor® under photoirradiation, which generates TEDA˙2+. A salient feature of our H-TEDA(BF 4) 2-promoted method is its flexibility to use the C(sp 3)-H precursor substrate as the limiting reactant, simplifying product isolations.

Source: Strathprints: The University of Strathclyde institutional repository (University of Strathclyde)

Authors: Yakubov, Shahboz, Barham, Joshua P.

Institutions: University of Regensburg, University of Strathclyde

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: Alexander von Humboldt-Stiftung, Deutsche Forschungsgemeinschaft, Bundesministerium für Bildung und Forschung, Elitenetzwerk Bayern

Awards: G1210188921, G1700615693, TRR 325: Kontrolle der chemischen Photokatalyse durch Molekülverbände

OpenAlex ID: W6986666199