Radical Coupling Initiated by Organophosphine Addition to Ynoates

Angew Chem Int Ed Engl. 2023 Jul 17;62(29):e202303869. doi: 10.1002/anie.202303869. Epub 2023 Jun 6.

Abstract

Dual nucleophilic phosphine photoredox catalysis is yet to be developed due to facile oxidation of the phosphine organocatalyst to the phosphoranyl radical cation. Herein, we report a reaction design that avoids this event and exploits traditional nucleophilic phosphine organocatalysis with photoredox catalysis to allow the Giese coupling with ynoates. The approach has good generality, while its mechanism is supported by cyclic voltametric, Stern-Volmer quenching, and interception studies.

Keywords: Dual Catalysis; Giese Reaction; Mechanistic Studies; Phosphine Organocatalysis; Photoredox Catalysis.