Murugesan, Kathiravan and Donabauer, Karsten and Konig, Burkhard (2021) Visible-Light-Promoted Metal-Free Synthesis of (Hetero)Aromatic Nitriles from C(sp(3))-H Bonds**. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 60 (5). pp. 2439-2445. ISSN 1433-7851, 1521-3773
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The metal-free activation of C(sp(3))-H bonds to value-added products is of paramount importance in organic synthesis. We report the use of the commercially available organic dye 2,4,6-triphenylpyrylium tetrafluoroborate (TPP) for the conversion of methylarenes to the corresponding aryl nitriles via a photocatalytic process. Applying this methodology, a variety of cyanobenzenes have been synthesized in good to excellent yield under metal- and cyanide-free conditions. We demonstrate the scope of the method with over 50 examples including late-stage functionalization of drug molecules (celecoxib) and complex structures such as l-menthol, amino acids, and cholesterol derivatives. Furthermore, the presented synthetic protocol is applicable for gram-scale reactions. In addition to methylarenes, selected examples for the cyanation of aldehydes, alcohols and oximes are demonstrated as well. Detailed mechanistic investigations have been carried out using time-resolved luminescence quenching studies, control experiments, and NMR spectroscopy as well as kinetic studies, all supporting the proposed catalytic cycle.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | HYDROGEN-ATOM TRANSFER; DIRECT C-H; TRANSITION-METALS; DIRECT CONVERSION; METHYL ARENES; ALCOHOLS; FUNCTIONALIZATION; ALKYLATION; ARYLATION; ALDEHYDES; ammoxidation; C− H functionalization; methylarenes; nitriles; photoredox catalysis |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Burkhard König |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 17 May 2021 15:49 |
| Last Modified: | 17 May 2021 15:49 |
| URI: | https://pred.uni-regensburg.de/id/eprint/43301 |
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