Synthesis of ( E )‐β‐ SF 5 ‐Styrenes via a Heck Reaction of in situ Generated Vinylsulfur Pentafluoride †

Comprehensive Summary The synthesis of ( E )‐(1‐alken‐1‐yl)pentafluoro‐λ 6 ‐sulfanes, a valuable class of compounds, is largely restricted to a single practical two‐step protocol that nonetheless suffers from several limitations, including functional‐group incompatibilities, imperfect stereoselectivity, and variable yields. In this study, we present a new approach for the synthesis of ( E )‐β‐SF 5 ‐styrenes via a Heck cross‐coupling reaction between aryl(hetero)iodides and in situ generated vinylsulfur pentafluoride. The triflate precursor, 2‐(pentafluoro‐λ 6 ‐sulfanyl)ethyl trifluoromethanesulfonate, is readily accessible. Notably, this method tolerates a broad range of substituents and furnishes the desired SF 5 ‐containing styrenes in a one‐pot protocol, as a single stereoisomer, and in moderate to good yields. More broadly, this work underscores the utility of vinylsulfur pentafluoride, an underused yet potentially versatile SF 5 ‐containing building block.