The anionic [2,3] sigmatropic Wittig rearrangements of deprotonated 4-hetera-1-pentenes and the anionic [3,3] sigmatropic Cope rearrangements of 3-substituted-1,5-hexadienes were explored by using density functional theory calculations. While the deprotonated anionic 3-hydroxy-1,5 hexadiene (2a), 3-thiohydroxy-1,5-hexadiene (2c), and 3-formamidyl-1,5-hexadiene (2d) Cope substrates undergo concerted rearrangements, the deprotonated anionic 3-amino-1,5-hexadiene (2b) and 3-methyl-1,5-hexadiene (2e) Cope substrates follow nonconcerted cleavage/recombination pathways. We have also found that the gas-phase Wittig (1a), aza-Wittig (1b), and carba-Wittig (1c) reactions proceed via nonconcerted cleavage/recombination pathways. These results are compared with previous results on the Cope rearrangements of deprotonated anionic 3-hydroxy-1,5-hexadiene and 3-amino-1,5-hexadiene anions. A previously established model that heterolytic and homolytic bond dissociation energies can be used to predict how anionic amino- and oxy-Cope substrates will react is generalized to account for the reactivity of other Cope substrates as well as for the Wittig rearrangements. There is also a relationship between the basicity of the anionic substituent in the Cope rearrangement and the reaction pathway: the more basic the substituent anion, the less stable it is, and the more likely it is that cleavage will occur. A first step toward studying these reactions in solution was also taken by calculating energetics for some of the rearrangements with a lithium counterion present.