We implement the dynamical Ising model on the large-scale architecture of white matter connections of healthy subjects in the age range 4–85 years, and analyze the dynamics in terms of the synergy, a quantity measuring the extent to which the joint state of pairs of variables is projected onto the dynamics of a target one. We find that the amount of synergy in explaining the dynamics of the hubs of the structural connectivity (in terms of degree strength) peaks before the critical temperature, and can thus be considered as a precursor of a critical transition. Conversely, the greatest amount of synergy goes into explaining the dynamics of more central nodes. We also find that the aging of structural connectivity is associated with significant changes in the simulated dynamics: There are brain regions whose synergy decreases with age, in particular the frontal pole, the subcallosal area, and the supplementary motor area; these areas could then be more likely to show a decline in terms of the capability to perform higher order computation (if structural connectivity was the sole variable). On the other hand, several regions in the temporal cortex show a positive correlation with age in the first 30 years of life, that is, during brain maturation. Author Summary In a previous study implementing the Ising model on a 2D lattice, we showed that the joint synergistic information shared by two variables on a target one peaks before the transition to an ordered state (critical point). Here we implemented the same model on individual structural connectomes, to answer these questions: - Does the synergy still peak before the critical point in a nonuniform network? - Are the hubs of structural connectivity also hubs of synergy? - Is there association with age? We found that synergy still peaks before the critical temperature and that hubs of structural connectivity are not among the nodes towards which synergy is highest. Furthermore, using robust measures of association we found both positive and negative associations of synergy with age, in localized clusters. In some regions this association is continuous with age; in others it is limited to around the first 30 years of age.