We report a fluoride-mediated nucleophilic aromatic amination of chloro-1H-1,2,3-triazolium salts with aliphatic amines. The reaction proceeded under mild reaction conditions to provide amino-1,2,3-triazolium salts with various functional groups, which can be utilized for further transformations. Moreover, it was found that an amino-1,2,3-triazolium salt was transformed via deprotonation into the N-heterocyclic imine (NHI), which exhibited the excellent catalytic activity for the cyanosilylation of acetophenone with trimethylsilyl cyanide.

1,2,3-Triazolium units are present in various functionalized molecules, including mesoionic carbenes, organocatalysts, and anion recognition receptors. While the oxidative [3 + 2] cycloaddition of triazenes with alkynes is one of the most efficient methods to construct the 1,2,3triazolium skeleton, the effect of reaction parameters and substrate scope in the reaction has not been fully studied. Herein, we developed a practical protocol for the synthesis of 1,2,3-triazolium salts and significantly expanded the substrate scope of triazenes and alkynes. Also, an efficient method for the deprotonative functionalization of 1,2,3-triazolium salts was achieved.

Herein, we developed a fluoride‐mediated nucleophilic aromatic amination of chloro‐1H‐1,2,3‐triazolium salts. Various functional groups were tolerated in this reaction, which enabled the synthesis of functionalized amino‐1H‐1,2,3‐triazolium salts. In addition, we investigated the catalytic properties of triazolium‐based N‐heterocyclic imines (NHIs) for cyanosilylation of ketones. The substituent was found to play a crucial role for inducing high catalytic activity.