Oxatriquinane and Oxatriquinacene: Extraordinary Oxonium Ions

Oxatriquinane, a fused, tricyclic alkyl oxonium ion of unprecented stability, was synthesized in five steps from 1,4,7-cyclononatriene. It survives reflux in H2O, chromatography, and attack by alcohols, alkyl thiols, halide ions, and hindered amine bases. The X-ray crystal structure shows longer C−O bond distances and more acute C−O−C bond angles than any reported alkyloxonium salt. The corresponding oxatriquinene and oxatriquinacene were also synthesized and represent the first examples of stable allyl oxonium species.