Scheme 1.

Synthesis of Ar‐SOF₃ from aryl halides. Reaction conditions: The Ar‐S‐Phth 3 was firstly synthesized based on the general methods from corresponding aryl halides. After purification through column chromatography, 3 (0.1 mmol), TCICA (0.9 mmol), KF (0.16 mmol), TFA (0.2 mmol) were stirred in MeCN (1 mL), RT for 24 h. Yields in parentheses correspond to those from Ar‐S‐Phth (based on ¹⁹F NMR spectra, PhCF₃ as internal standard); yields outside the parenthesis correspond to those from 1. [a] Reaction conditions: 3 s was prepared from the reaction of N‐chlorophthalimide with 2‐pyrimidinethiol.