Quantum chemical calculations can afford valuable information to understand the chemical processes and the structural features of chemical species. This tool
has become very informative, and several aspects can be discussed on the thioamides
under a theoretical point of view such as the effects of structure in their planarity
and some cases with derivations of that planarity, C–N bond rotation in comparison to the related amides and selenoamides and implications in the transition state,
and the influence of the solvent or the influence of remote substituents. This review
will deal as well with isomerization processes such as tautomerization or rotation of
N-bonded methyl groups. Some aspects of reactivity of thioamides such as the bonddissociation enthalpy (BDE) or their behavior as radical scavengers are discussed as
well. Some comments on the theoretical aspects of thiopeptides are briefly analyzed.
