• Media type: E-Article
  • Title: Strain‐Release Pentafluorosulfanylation and Tetrafluoro(aryl)sulfanylation of [1.1.1]Propellane: Reactivity and Structural Insight**
  • Contributor: Kraemer, Yannick; Ghiazza, Clément; Ragan, Abbey N.; Ni, Shengyang; Lutz, Sigrid; Neumann, Elizabeth K.; Fettinger, James C.; Nöthling, Nils; Goddard, Richard; Cornella, Josep; Pitts, Cody Ross
  • Published: Wiley, 2022
  • Published in: Angewandte Chemie International Edition, 61 (2022) 48
  • Language: English
  • DOI: 10.1002/anie.202211892
  • ISSN: 1521-3773; 1433-7851
  • Origination:
  • Footnote:
  • Description: AbstractWe leveraged the recent increase in synthetic accessibility of SF5Cl and Ar−SF4Cl compounds to combine chemistry of the SF5and SF4Ar groups with strain‐release functionalization. By effectively adding SF5and SF4Ar radicals across [1.1.1]propellane, we accessed structurally unique bicyclopentanes, bearing two distinct elements of bioisosterism. Upon evaluating these “hybrid isostere” motifs in the solid state, we measured exceptionally short transannular distances; in one case,the distance rivals the shortest nonbonding C⋅⋅⋅C contact reported to date. This prompted SC‐XRD and DFT analyses that support the notion that a donor‐acceptor interaction involving the “wing” C−C bonds is playing an important role in stabilization. Thus, these heretofore unknown structures expand the palette for highly coveted three‐dimensional fluorinated building blocks and provide insight to a more general effect observed in bicyclopentanes.