A mild, rapid, and regioselective cyclization of azidofluoroalkanes with carbonyl-stabilized phosphonium ylides, resulting in the formation of 1-fluoroalkyl-5-substituted-1,2,3-triazoles, is presented. The synthetic method tolerates air and water, works at room temperature in a benign solvent, and is metal-free. Both starting materials are commercially available and easily prepared. The cyclization method was expanded to 4-halogen-substituted analogues of target triazoles, which underwent either rhodium-catalyzed transannulation with benzonitrile to yield uniquely substituted N-fluoroalkylated 4-haloimidazoles or cross-coupling reactions to produce fully substituted N-fluoroalkylated triazoles.

Charles University Faculty of Science Albertov 6 Prague 128 00 Czechia

Department of Physical Chemistry University of Chemistry and Technology Technická 5 Prague 166 28 Czechia

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nám 2 Prague 160 00 Czechia

Institute of Organic Chemistry and Technology University of Pardubice Studentská 573 Pardubice 532 10 Czechia

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