A rhodium-catalyzed transannulation via ring-opening of N-(per)fluoroalkyl-substituted 1,2,3-triazoles followed by cycloaddition with different nitriles, enol ethers, isocyanates and silyl ketene acetals under microwave heating provided a highly efficient route to previously unreported N-(per)fluoroalkyl-substituted imidazoles, pyrroles, imidazolones and pyrrolones, respectively. These reactions were found to be applicable to the synthesis of a variety of 5-membered heterocycles bearing different (per)fluoroalkyl substituents as well as both electron-donating and electron-withdrawing groups attached to the heterocyclic core.

N-Fluoroalkylated 1,2,3-triazoles in the presence of triflic acid or fluorosulfonic acid underwentacascade reactionc onsisting of triazole protonation, ring opening, nitrogene limination, sulfonate addition, HF elimination, and hydrolysis to furnish novel trifluoromethanesulfonyloxy-or fluorosulfonyloxy-substituted enamides, respectively,i nahighly stereoselective fashion. The vinyl triflates underwent cross-coupling reactions to av ariety of substituted enamidesa nd serve as sourceso ft he aminovinyl cations. In reactions with triflic acid, electron-rich triazoles afforded2 -fluoroalkylated oxazoles. 2( CzechRepublic) [c] V. Motornov HigherChemical College, D. I. Mendeleev Universityo fthe Chemical Technologyo fRussia, Miusskaya sq.9,Moscow 125047 (Russia) Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.