Toluene Dioxygenase‐Catalysed Oxidation of Benzyl Azide to Benzonitrile: Mechanistic Insights for an Unprecedented Enzymatic Transformation |
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| Authors: | María Agustina Vila Mariana Pazos César Iglesias Dr. Nicolás Veiga Dr. Gustavo Seoane Dr. Ignacio Carrera |
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| Affiliation: | 1. Departamento de Química Orgánica, Facultad de Química, Universidad de la República, Montevideo, Uruguay;2. Cátedra de Microbiología, Departamento de Biociencias, Facultad de Química, Universidad de la República, Montevideo, Uruguay;3. Cátedra de Química Inorgánica, Departamento Estrella Campos, Facultad de Química, Universidad de la República., Montevideo, Uruguay;4. http://www.secobi.fq.edu.uy/ |
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| Abstract: | Enzymatic dioxygenation of benzyl azide by toluene dioxygenase (TDO) produces significant amounts of the cis‐cyclohexadienediol derived from benzonitrile, along with the expected azido diols. We demonstrate that TDO catalyses the oxidation of benzyl azide to benzonitrile, which is further dioxygenated to produce the observed cis‐diol. A proposed mechanism for this transformation involves initial benzylic monooxygenation followed by a nitrene‐mediated rearrangement to form an oxime, which is further dehydrated to afford the nitrile. To the best of our knowledge, this is the first report of enzymatic oxidation of an alkyl azide to a nitrile. In addition, the described oxime‐dehydration activity has not been reported for Rieske dioxygenases. |
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| Keywords: | azides biocatalysis dioxygenases oxidation Rieske |
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