Chemoselective Hydro(Chloro)pentafluorosulfanylation of Diazo Compounds with Pentafluorosulfanyl Chloride.

Pentafluorosulfanyl chloride (SF 5 Cl) is the most prevalent reagent for the incorporation of SF 5 group into organic compounds. However, the preparation of SF 5 Cl often relied on hazardous reagents and specialized apparatuses. Herein we described a safe and practical synthesis of a bench-stable and easy-to-handle solution of SF 5 Cl in n -hexane under gas-reagent-free conditions. The synthetic application of SF 5 Cl was demonstrated through the unprecedented reaction with diazo compounds. The chemoselective hydro- and chloropentafluorosulfanylations of α-diazo carbonyl compounds were developed in the presence of K 3 PO 4 or copper catalyst respectively. These reactions provide a direct and efficient access to various α-pentafluorosulfanyl carbonyl compounds of high value for potential applications.