RESUMEN
We leveraged the recent increase in synthetic accessibility of SF5 Cl and Ar-SF4 Cl compounds to combine chemistry of the SF5 and SF4 Ar groups with strain-release functionalization. By effectively adding SF5 and SF4 Ar 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 Câ â â 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.
RESUMEN
The catalytic activity of a highly reduced Ni catalyst in the context of a Kumada-Corriu cross-coupling has been studied. This nickel complex is characterized by its high electron density, stabilized by simple olefin ligands in combination with two Li ions. Landmark reactivity has been found with this precatalyst which operates at cryogenic temperatures, thus allowing the presence of sensitive functionalities. Structural elucidation of oxidative addition intermediates and their reactivity suggest highly reduced species being operative in the C-C bond forming event.