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Synthesis of 5-Iodo-1,4-disubstituted-1,2,3-triazoles Mediated by in Situ Generated Copper(I) Catalyst and Electrophilic Triiodide Ion

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posted on 20.02.2016, 15:36 by Wendy S. Brotherton, Ronald J. Clark, Lei Zhu
Mixing copper­(II) perchlorate and sodium iodide solutions results in copper­(I) species and the electrophilic triiodide ions, which collectively mediate the cycloaddition reaction of organic azide and terminal alkyne to afford 5-iodo-1,4-disubstituted-1,2,3-triazoles. One molar equivalent of an amine additive is required for achieving a full conversion. Excessive addition of the amine compromises the selectivity for 5-iodo-1,2,3-triazole by promoting the formation of 5-proto-1,2,3-triazole. Based on preliminary kinetic and structural evidence, a mechanistic model is formulated in which a 5-iodo-1,2,3-triazole is formed via iodination of a copper­(I) triazolide intermediate by the electrophilic triiodide ions (and possibly triethyliodoammonium ions). The experimental evidence explains the higher reactivity of the in situ generated copper­(I) species and triiodide ion in the formation of 5-iodo-1,2,3-triazoles than that of the pure forms of copper­(I) iodide and iodine.