Exploiting non-covalent π interactions for catalyst design

Molecular recognition, binding and catalysis are often mediated by non-covalent interactions involving aromatic functional groups. Although the relative complexity of these so-called π interactions has made them challenging to study, theory and modelling have now reached the stage at which we can explain their physical origins and obtain reliable insight into their effects on molecular binding and chemical transformations. This offers opportunities for the rational manipulation of these complex non-covalent interactions and their direct incorporation into the design of small-molecule catalysts and enzymes. Our increasing understanding of non-covalent interactions involving aromatic systems is reviewed, and the use of these insights in the design of small-molecule catalysts and enzymes is surveyed. Non-covalent interactions involving aromatic systems play an important part in molecular recognition and binding. Dean Toste and colleagues survey our growing understanding of the physical factors that govern these complex interactions and examine how such interactions influence chemical transformations. The insights gained from computational and empirical studies make it increasingly possible to incorporate such subtle non-covalent interactions into the design of small-molecule catalysts and enzymes.