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

• Published in: ChemPlusChem (Weinheim, Germany) Germany), 2024-08, Vol.89 (8), p.e202400168-n/a
• Main Authors: Kucher, Hannes, Wenzel, Jonas O., Rombach, David
• Format: Article
• Language: English
• Subjects: acetylene; hydrothiolation; organofluorine chemistry; pentafluorosulfanyl group; TASP; vinylsulfides
• ISSN: 2192-6506; 2192-6506
• DOI: 10.1002/cplu.202400168

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. Triisopropylsilyl acetylene sulfur pentafluoride (TASP) has been suggested as a precious reagent to facilitate access to novel SF5‐containing building blocks for synthetic chemistry. Herein, we report a robust hydrothiolation protocol to access the so far elusive class of terminal Z‐configured β‐SF5 vinyl sulfides. This robust and clean method (up to 99 % yield) shows excellent (Z)‐selectivity and functional group tolerance, employing bench‐stable reagents under atmospheric reaction conditions.