Hydrothiolation of Triisopropylsilyl Acetylene Sulfur Pentafluoride – Charting the Chemical Space of β‐SF5 Vinyl Sulfides.

Recently, we suggested liquid and high‐boiling TIPS‐CC‐SF5 (TASP) as a versatile reagent to access so far elusive SF5‐containing building blocks by less specialized laboratories under bench‐top conditions. The synthesis of non‐aromatic SF5 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. [ABSTRACT FROM AUTHOR]