9‐Azahomocubane

Homocubane, a highly strained cage hydrocarbon, contains two very different positions for the introduction of a nitrogen atom into the skeleton, e. g., a position 1 exchange results in a tertiary amine whereas position 9 yields a secondary amine. Herein reported is the synthesis of 9‐azahomocubane along with associated structural characterization, physical property analysis and chemical reactivity. Not only is 9‐azahomocubane readily synthesized, and found to be stable as predicted, the basicity of the secondary amine was observed to be significantly lower than the structurally related azabicyclo[2.2.1]heptane, although similar to 1‐azahomocubane. 9‐Azahomocubane is unique amongst the nitrogen derivatives of homocubane, as it contains a secondary nitrogen atom, which can be used as a building block through amide bond formation. Herein reported is the first synthesis of 9‐azahomocubane, which was achieved via a rarely utilized Stieglitz rearrangement, and confirmed by X‐ray crystal structure analysis. The chemical stability of 9‐azahomocubane exceeds that of the 1‐azahomocubane, as predicted, although the basicity and calculated strain energy are similar.