Photogeneration of Chlorine Radical from a Self-Assembled Fluorous 4CzIPN •Chloride Complex: Application in C-H bond Functionalization

Angew Chem Int Ed Engl. 2024 Apr 18:e202402964. doi: 10.1002/anie.202402964. Online ahead of print.ABSTRACTThe chlorine radical is a strong HAT (Hydrogen Atom Transfer) agent that is very useful for the functionalization of C(sp3)-H bonds. Albeit highly attractive, its generation from the poorly oxidizable chloride ion mediated by an excited photoredox catalyst is a difficult task. We now report that 8Rf8-4CzIPN, an electron-deficient fluorous derivative of the benchmark 4CzIPN photoredox catalyst belonging to the donor-acceptor carbazole-cyanoarene family, is not only a better photooxidant than 4CzIPN, but also becomes an excellent host for the chloride ion. Combining these two properties ultimately makes the self-assembled 8Rf8-4CzIPN•Cl- dual catalyst highly reactive in redox-neutral Giese-type C(sp3)-H bond alkylation reactions promoted by the chlorine radical. Additionally, because of its fluorous character, the efficient separation/recovery of 8Rf8-4CzIPN could be envisioned.PMID:38634355 | DOI:10.1002/anie.202402964

Source: Angewandte Chemie - April 18, 2024 Category: Chemistry Authors: Victor Carr é Pascale Godard Rapha ël Méreau Henri-Pierre Jacquot de Rouville Gediminas Jonusauskas Nathan McClenaghan Thierry Tassaing Jean-Marc Vincent Source Type: research