{"id":9604,"date":"2012-11-23T09:32:30","date_gmt":"2012-11-23T08:32:30","guid":{"rendered":"https:\/\/web.computaex.es\/?page_id=9604"},"modified":"2025-08-27T09:42:24","modified_gmt":"2025-08-27T07:42:24","slug":"an-experimental-and-computational-assessment-of-acid-catalyzed-azide-nitrile-cycloadditions","status":"publish","type":"page","link":"https:\/\/computaex.es\/en\/publicaciones\/an-experimental-and-computational-assessment-of-acid-catalyzed-azide-nitrile-cycloadditions\/","title":{"rendered":"An Experimental and Computational Assessment of Acid-Catalyzed Azide-Nitrile Cycloadditions"},"content":{"rendered":"
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David Cantillo, Bernhard Gutmann, and C. Oliver Kappe.\u00a0An Experimental and Computational Assessment of Acid-Catalyzed Azide-Nitrile Cycloadditions<\/strong>. The Journal of Organic Chemistry. Noviembre, 2012. DOI: 10.1021\/jo3022742<\/p>\n

Abstract<\/span><\/p>\n

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\"Abstract<\/div>\n

The mechanism of the azide\u2013nitrile cycloaddition mediated by different Br\u00f8nsted and Lewis acids has been addressed through DFT calculations. In all cases activation of the nitrile substrate by the Br\u00f8nsted or Lewis acid catalyst was found to be responsible for the rate enhancement. According to DFT calculations the cycloaddition proceeds in a stepwise fashion involving the initial formation of an open-chain imidoyl azide intermediate. Kinetic experiments performed using\u00a0N<\/i>-methyl-2-pyrrolidone as solvent and sodium azide as azide source demonstrate that all evaluated Br\u00f8nsted acids have the same efficiency toward cycloaddition with benzonitrile, suggesting that hydrazoic acid is the actual dominant catalytic species in these tetrazole syntheses. Lewis acids such as Zn or Al salts perform in a similar manner, activating the nitrile moiety and leading to an open-chain intermediate that subsequently cyclizes to produce the tetrazole nucleus. The most efficient catalyst evaluated was 5-azido-1-methyl-3,4-dihydro-2H<\/i>-pyrrolium azide, which can readily be generated in situ from aluminum chloride, sodium azide in\u00a0N<\/i>-methyl-2-pyrrolidone. The efficiency of this catalyst has been examined by preparation of a series of 5-substituted-1H<\/i>-tetrazoles. The desired tetrazole structures were obtained in high yields within 3\u201310 min employing controlled microwave heating.<\/p>\n<\/div>\n<\/div>\n<\/div>\n<\/div>\n

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