A reaction between azide, alkyne and 2H-azirine resulted in C-C bond formation at position five of 1,2,3-triazole, instead of previously misidentified C-N bond connectivity. The reaction mechanism of this C-C bond formation on the triazole ring was fully explained by employing calibrated QM(DFT-D3) calculations. Functionalization of primary products provided substituted pyrimidine, furan or 1,3-oxazepine.

Department of Organic Chemistry Faculty of Science Charles University Hlavova 2030 8 CZ 128 43 Prague 2 Czech Republic

Institute of Organic Chemistry and Biochemistry Academy of Sciences of the Czech Republic Flemingovo nám 2 166 10 Prague Czech Republic

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