Induced Intramolecularity: An Effective Strategy in Catalysis

The use of reversibly formed covalent bonds to induce intramolecular reactions is a powerful way of controlling regio- and stereoselectivity, as well as accelerating reactions. Although this mode of activation was demonstrated in catalytic systems over 60 years ago, it is infrequently used in catalyst design. This review will focus on highlighting examples of reversible covalent bonding in organic catalysts as well as ligands for metal catalysis. A key aspect of this type of catalysis is that it is an entropically driven process, so it has the potential to be applied to a broad variety of reactions. Furthermore, this design element can be used in concert with more traditional forms of catalyst activation.