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Mechanochemical Access to Functional Clickates with Nitro-Retentive Selectivity via Organocatalyzed Oxidative Azide-Olefin Cycloaddition

Murugan Vadivelu, Abbasriyaludeen Abdul Raheem, John Paul Raj, Jebamalai Elangovan, Kesavan Karthikeyan* and Chandrasekar Praveen*

*B. S. Abdur Rahman Crescent Inst. of Science and Technology, Chennai 600048; Central Electrochemical Research Inst., Karaikudi 630003, India, Email: karthiclrigmail.com, chandrasekar.praveengmail.com

M. Vadivelu, A. A. Raheem, J. P. Raj, J. Elangovan, K. Karthikeyan, C. Praveen, J. Sun, Org. Lett., 2022, 24, 2798-2803.

DOI: 10.1021/acs.orglett.2c00621



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Abstract

A mechanochemical route enables a selective synthesis of 4-nitro-1,2,3-triazoles via organocatalyzed oxidative [3 + 2] cycloaddition between β-nitrostyrenes and organic azides. The reaction features a nontoxic catalyst, catalyst recyclability, no rigorous solvent-extraction, no toxic byproducts, atmospheric oxygen as oxidant, and scalability to gram-scale.

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proposed mechanism



Safety

Whenever organic azides are handled; care should be exercised as they may explode with little input of external energy. However, we did not encounter any explosive decomposition using our conditions, probably because of the greater number of carbon atoms compared to nitrogen atoms. Moreover, we did not choose acyl azides or vinyl azides for our work as they should not be warmed without toluene or similar low-pressure solvent. Nevertheless, all benzylic type azides used in this study were stored at 5C and used only during the reaction.


Key Words

1,2,3-triazoles, mechanochemistry, organocatalysis


ID: J54-Y2022