We report the voyage of two flat, highly unsaturated systems into the third dimension. Specifically, we investigated the 1,3-dipolar cycloadditions of 9-diazofluorene with a rapidly growing class of strained dipolarophile—biarylcyclooctynes. We found that the initial spirocyclic 3H-pyrazole cycloadducts are isolable, and can be subjected to controllable [1,5]-sigmatropic shifts. These van Alphen–Hüttel rearrangements generate either the metastable 4H-pyrazoles—another spirocyclic fused-ring system with a highly contorted structure—or the thermodynamically favored 1H-pyrazoles. The 1H-pyrazoles display extended conjugation and can be classified as [5]-helicenes containing a phenanthro-pyrazole fused to a dihydro-cyclooctatetraene. Overall, these studies provide a modular framework to control heteroatom placement, ring size, and ring fusion in the syntheses of carbon-rich materials.