期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 5, 页码 2439-2445出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202011815
关键词
ammoxidation; C− H functionalization; methylarenes; nitriles; photoredox catalysis
资金
- German Science Foundation (DFG) [KO 1537/18-1]
- European Research Council (ERC) under the European Union [741623]
- Projekt DEAL
- European Research Council (ERC) [741623] Funding Source: European Research Council (ERC)
The study demonstrates the use of the commercially available organic dye TPP for the photocatalytic conversion of methylarenes to aryl nitriles, providing a wide range of cyanobenzenes under metal- and cyanide-free conditions. The presented synthetic protocol is applicable for gram-scale reactions and includes detailed mechanistic investigations supporting the proposed catalytic cycle.
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.
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