Steric effects on intramolecular reactivity in cyclic dipeptides: Conformational analysis validated by a combined MD/DFT approach

► Validation procedure for MD simulations of short peptides established. ► Correlation of intramolecular dynamics and reactivity within combined MD/DFT concept. ► Successful experimental cross-validation of theoretical results. ► Intramolecular HAT reactivity predictable from MD simulations.