The rationale behind using heterocyclic compounds [1], particularly nitrogen heterocycles, as higher energy insensitive high explosives is discussed, including the potential advantages compared with carbocyclic compounds. The types of functional groups used to impart energy to heterocyclic nuclei, whilst maintaining insensitivity, and methodologies for their introduction, are covered. The latter include nitration (by conventional and clean synthetic methods), amination, and oxidation (on ring heteroatoms and of exocyclic amino groups). Strategies for maximising the energetic content of a given heterocyclic nucleus are also examined. The syntheses of specific examples at QinetiQ are described, based on the following nuclei: pyridine, pyrimidine, pyrazine, quinoxaline, quinazoline, pteridine and purine. Strategies for obtaining the desired amino-nitro derivatives and their heterocyclic N-oxides are outlined. Optimisation of the synthetic routes for several candidates is discussed. The physical, explosive and thermal properties of the more successful candidates are described, with suggestions for their potential application in military stores.