The hydrothiolation of TIPS-CΞC-SF5 – Charting the chemical space of beta-SF5 vinyl sulfides

08 November 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The pentafluorosulfanyl group is suggested to be a promising candidate adding to the toolbox of emerging fluorinated motifs. While the synthesis of non-aromatic SF5 bulding blocks generally requires on-site fluorination or pentafluorosulfanylation steps employing toxic and/or gaseous reagents, downstream processing of commercially available prefunctionalized molecules is proposed as an alternative strategy to allow access to this motif by less specialized laboratories. Herein, we report a benign bench-top protocol for the synthesis of Z-configured beta-pentafluorosulfanylated vinyl sulfides in good to excellent yields with excellent Z-diasteroselectivity and broad functional group tolerance. This general method exploits an in-situ protodesilylation-hydrothiolation sequence of commercially available liquid and high-boiling TIPS-CΞC-SF5 (TASP). This so far uncharted class of compounds was analyzed 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.


vinyl sulfides


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