Hydrothiolation of Triisopropylsilyl Acetylene Sulfur Pentafluoride - Charting the Chemical Space of β-SF Vinyl Sulfides.

Recently, we suggested liquid and high-boiling TIPS-CC-SF (TASP) as a versatile reagent to access so far elusive SF-containing building blocks by less specialized laboratories under bench-top conditions. The synthesis of non-aromatic SF building blocks generally requires on-site fluorination or pentafluorosulfanylation steps employing toxic and/or gaseous reagents. Herein, we underline the versatility of this reagent by reporting a benign bench-top protocol for the synthesis of Z-configured β-pentafluorosulfanylated vinyl sulfides in good to excellent yields (up to 99 %) with exclusive (Z)-diasteroselectivity and broad functional group tolerance. This method exploits an in-situ protodesilylation-hydrothiolation sequence. This so far uncharted class of compounds was characterized by means of NMR-spectroscopy as well as SC-XRD. Furthermore, we suggest the reaction to proceed via a kinetically controlled closed-shell reaction pathway, corroborated by in-silico experiments.