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

Autor: Carré V; Institut des Sciences Moléculaires, CNRS UMR 5255, Université de Bordeaux, 351, Crs de la Libération, 33405, Talence, France., Godard P; Institut des Sciences Moléculaires, CNRS UMR 5255, Université de Bordeaux, 351, Crs de la Libération, 33405, Talence, France., Méreau R; Institut des Sciences Moléculaires, CNRS UMR 5255, Université de Bordeaux, 351, Crs de la Libération, 33405, Talence, France., Jacquot de Rouville HP; Institut de Chimie de Strasbourg, CNRS UMR 7177, Université de Strasbourg, 4, rue Blaise Pascal, 67000, Strasbourg, France., Jonusauskas G; Laboratoire Ondes et Matière d'Aquitaine, CNRS UMR 5798, Univ. Bordeaux, 351, Crs de la Libération, 33405, Talence, France., McClenaghan N; Institut des Sciences Moléculaires, CNRS UMR 5255, Université de Bordeaux, 351, Crs de la Libération, 33405, Talence, France., Tassaing T; Institut des Sciences Moléculaires, CNRS UMR 5255, Université de Bordeaux, 351, Crs de la Libération, 33405, Talence, France., Vincent JM; Institut des Sciences Moléculaires, CNRS UMR 5255, Université de Bordeaux, 351, Crs de la Libération, 33405, Talence, France.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Jun 21; Vol. 63 (26), pp. e202402964. Date of Electronic Publication: 2024 May 21.
DOI: 10.1002/anie.202402964
Abstrakt: The chlorine radical is a strong HAT (Hydrogen Atom Transfer) agent that is very useful for the functionalization of C(sp 3 )-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 8R f8 -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 8R f8 -4CzIPN•Cl - dual catalyst highly reactive in redox-neutral Giese-type C(sp 3 )-H bond alkylation reactions promoted by the chlorine radical. Additionally, because of its fluorous character, the efficient separation/recovery of 8R f8 -4CzIPN could be envisioned.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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