Macromolecular Engineering of Biodegradable Polyesters by Ring‐Opening Polymerization and ‘Click’ Chemistry

Biodegradability makes aliphatic polyesters valuable candidates for biomaterials and environmentally friendly thermoplastics. Nevertheless, their chemical modification, which is mandatory for a series of potential applications, is usually a problem because it must be carried out under very mild conditions in order to prevent degradation by hydrolysis and/or transesterification from occurring. In this review, the copper( I )‐catalyzed azide–alkyne cycloaddition, which is a click reaction, is shown to be very efficient to bypass these problems and to tailor the macromolecular architecture and functionality of those polyesters without facing undesired degradation reactions.