Photoinitiated <i>anti</i>‐Hydropentafluorosulfanylation of Terminal Alkynes

Abstract

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 : &gt;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.

Topics & Concepts