Dehydrogenative Anodic Cyanation Reaction of Phenols in Benzylic Positions
Johannes L. Röckl
Institute of Organic Chemistry, Duesbergweg 10–14, 55128 Mainz, Germany
Graduate School Materials Science in Mainz, Johannes Gutenberg Universität Mainz, Staudinger Weg 9, 55128 Mainz, Germany
Search for more papers by this authorYasushi Imada
Department of Applied Biological Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo, 183-8509 Japan
Graduate School Materials Science in Mainz, Johannes Gutenberg Universität Mainz, Staudinger Weg 9, 55128 Mainz, Germany
Search for more papers by this authorProf. Dr. Kazuhiro Chiba
Department of Applied Biological Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo, 183-8509 Japan
Search for more papers by this authorProf. Dr. Robert Franke
Evonik Performance Materials GmbH, Paul-Baumann-Str. 1, 45772 Marl, Germany
Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, Universitätstraße 150, 44801 Bochum, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Siegfried R. Waldvogel
Institute of Organic Chemistry, Duesbergweg 10–14, 55128 Mainz, Germany
Graduate School Materials Science in Mainz, Johannes Gutenberg Universität Mainz, Staudinger Weg 9, 55128 Mainz, Germany
Search for more papers by this authorJohannes L. Röckl
Institute of Organic Chemistry, Duesbergweg 10–14, 55128 Mainz, Germany
Graduate School Materials Science in Mainz, Johannes Gutenberg Universität Mainz, Staudinger Weg 9, 55128 Mainz, Germany
Search for more papers by this authorYasushi Imada
Department of Applied Biological Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo, 183-8509 Japan
Graduate School Materials Science in Mainz, Johannes Gutenberg Universität Mainz, Staudinger Weg 9, 55128 Mainz, Germany
Search for more papers by this authorProf. Dr. Kazuhiro Chiba
Department of Applied Biological Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo, 183-8509 Japan
Search for more papers by this authorProf. Dr. Robert Franke
Evonik Performance Materials GmbH, Paul-Baumann-Str. 1, 45772 Marl, Germany
Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, Universitätstraße 150, 44801 Bochum, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Siegfried R. Waldvogel
Institute of Organic Chemistry, Duesbergweg 10–14, 55128 Mainz, Germany
Graduate School Materials Science in Mainz, Johannes Gutenberg Universität Mainz, Staudinger Weg 9, 55128 Mainz, Germany
Search for more papers by this authorGraphical Abstract
An electrochemically driven installation of cyano moieties to valuable chemical building blocks via anodic oxidation is presented. The reactive intermediates can be reacted with cyanides to obtain valuable 2-phenylacetonitriles in a facile, protective group-free, metal-free and environmentally-friendly manner. Additionally, the reaction is easily scalable and inherently safe.
Abstract
The selective dehydrogenative electrochemical activation of benzylic positions by 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) and subsequent cyanation is presented for the first time. Herein, we report a sustainable, scalable, and metal-free dehydrogenative benzylic cyanation protocol. Valuable 2-phenylacetonitrile derivatives are accessible in the presence of a cyanide source and an electrolytically-derived HFIP ether. The direct application of electricity enables a safe and environmentally benign chemical transformation, since oxidizers are replaced by electricity.
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