The energy landscapes of highly strained cyclomethines and their aza analogs have been investigated in detail at the aug-cc-pVDZ and 6-311++G** levels of theory using density functional theory (DFT). We optimized the heat of formation, bond lengths, vibrational frequencies, and Mulliken charge distributions of representative small polycyclic systems, namely tetrahedrane, prismane, and cubane. The delocalization and electron-withdrawing effects of aza substitution are reflected in the results, which show that adding nitrogen to
cyclomethine frameworks improves overall thermodynamic stability. Oddly, these aza derivatives are more energetically beneficial since they have lower heat of formation than their parent hydrocarbons while also showing higher electronic stability. Apart from energy characterisation, pericyclic reaction pathways using simple diatomic precursors (C≡ C, C≡ N, and N≡ N) were used to investigate the in-silico synthetic feasibility ofthese strained molecules. These aza analogs might theoretically be formed from molecular synthons via
coordinated cycloaddition pathways, according to transition state searches and reaction path calculations. In contrast to solely hydrocarbon systems, nitrogen insertion lowers the activation barriers.