We leveraged the recent increase in synthetic accessibility of SF 5 Cl and ArÀ SF 4 Cl compounds to combine chemistry of the SF 5 and SF 4 Ar groups with strain-release functionalization. By effectively adding SF 5 and SF 4 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 C•••C contact reported to date. This prompted SC-XRD and DFT analyses that support the notion that a donoracceptor interaction involving the "wing" CÀ 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.
The fundamental challenge of C−F bond formation by reductive elimination has been met by compounds of select transition metals and fewer main group elements. The work detailed herein expands the list of main group elements known to be capable of reductively eliminating a C−F bond to include tellurium. Surprising and novel modes of both sp2 and sp3 C−F bond formation were observed alongside formation of TeIV cations during two separate attempts to synthesize/characterize fluorinated organotellurium(VI) cations in superacidic media (SbF5/SO2ClF). Following detailed low‐temperature NMR experiments, the mechanisms of the two unique reductive elimination reactions were probed and investigated using density functional theory (DFT) calculations. Ultimately, we found that an “indirect” reductive elimination pathway is likely operative whereby Sb plays a key role in fluoride abstraction and C−F bond formation, as opposed to unimolecular reductive elimination from a discrete TeVI cation.
We leveraged the recent increase in synthetic accessibility of SF5Cl and Ar-SF4Cl compounds to combine chemistry of the SF5 and SF4Ar groups with strain-release functionalization. By effectively adding SF5 and 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.
We leveraged the recent increase in synthetic accessibility of SF 5 Cl and ArÀ SF 4 Cl compounds to combine chemistry of the SF 5 and SF 4 Ar groups with strain-release functionalization. By effectively adding SF 5 and SF 4 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 C•••C contact reported to date. This prompted SC-XRD and DFT analyses that support the notion that a donoracceptor interaction involving the "wing" CÀ 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.
The fundamental challenge of CÀ F bond formation by reductive elimination has been met by compounds of select transition metals and fewer main group elements. The work detailed herein expands the list of main group elements known to be capable of reductively eliminating a CÀ F bond to include tellurium. Surprising and novel modes of both sp 2 and sp 3 CÀ F bond formation were observed alongside formation of Te IV cations during two separate attempts to synthesize/ characterize fluorinated organotellurium(VI) cations in superacidic media (SbF 5 /SO 2 ClF). Following detailed low-temperature NMR experiments, the mechanisms of the two unique reductive elimination reactions were probed and investigated using density functional theory (DFT) calculations. Ultimately, we found that an "indirect" reductive elimination pathway is likely operative whereby Sb plays a key role in fluoride abstraction and CÀ F bond formation, as opposed to unimolecular reductive elimination from a discrete Te VI cation.
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