Petzold, Daniel and Nitschke, Philipp and Brandl, Fabian and Scheidler, Veronica and Dick, Bernhard and Gschwind, Ruth M. and Koenig, Burkhard (2019) Visible-Light-Mediated Liberation and In Situ Conversion of Fluorophosgene. CHEMISTRY-A EUROPEAN JOURNAL, 25 (1). pp. 361-366. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
The first example for the photocatalytic generation of a highly electrophilic intermediate that is not based on radical reactivity is reported. The single-electron reduction of bench-stable and commercially available 4-(trifluoromethoxy)benzonitrile by an organic photosensitizer leads to its fragmentation into fluorophosgene and benzonitrile. The in situ generated fluorophosgene was used for the preparation of carbonates, carbamates, and urea derivatives in moderate to excellent yields via an intramolecular cyclization reaction. Transient spectroscopic investigations suggest the formation of a catalyst charge-transfer complex-dimer as the catalytic active species. Fluorophosgene as a highly reactive intermediate, was indirectly detected via its next downstream carbonyl fluoride intermediate by NMR. Furthermore, detailed NMR analyses provided a comprehensive reaction mechanism including a water dependent off-cycle equilibrium.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | PHOTOREDOX CATALYSIS; ELECTRON; PHOTOCATALYSIS; PERSPECTIVES; REDUCTION; CT-complex; fluorophosgene; NMR spectroscopy; photocatalysis; trifluoromethoxyarenes |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Burkhard König |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 21 Apr 2020 05:10 |
| Last Modified: | 21 Apr 2020 05:10 |
| URI: | https://pred.uni-regensburg.de/id/eprint/27746 |
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