Synthesis of 5-iodo-1,4-disubstituted-1,2,3-triazoles mediated by in situ generated copper(I) catalyst and electrophilic triiodide ion.
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.
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA.
Wendy S
WS
Brotherton
Ronald J
RJ
Clark
Lei
L
Zhu
D000480:Alkynes / Q000737:chemistry; D001386:Azides / Q000737:chemistry; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D003500:Cyclization; D007454:Iodides / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D015394:Molecular Structure; D014230:Triazoles / Q000138:chemical synthesis* / Q000737:chemistry
D000480:Alkynes; D001386:Azides; D007454:Iodides; D007477:Ions; D014230:Triazoles; D003300:Copper