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Abstract A photoinitiated anti ‐hydropentafluorosulfanylation of terminal alkynes using SF 5 Cl and (TMS) 3 SiH as the hydrogen atom donor is reported. This transformation generates selectively ( Z )‐(1‐alken‐1‐yl)pentafluoro‐λ 6 ‐sulfanes ( Z : E : >85:15), thus allowing the preparation of this previously unknown geometrical isomer. DFT calculations highlight that the selectivity is due to the intrinsic preference of SF 5 ‐substituted vinylic radicals to adopt a cis geometry, and to increased steric contacts during the transition structures leading to the minor ( E )‐products.
Birepinte et al. (Sat,) studied this question.