New Prospects for the Grafting of Functional Groups onto Aliphatic Polyesters. Ring‐Opening Polymerization of α‐ or γ‐Substituted ε‐Caprolactone Followed by Chemical Derivatization of the Substituents

Recent progress in the synthesis of aliphatic polyesters, substituted by pendent functional groups, has been reviewed. Two main strategies have to be distinguished. The first route consists of the ring‐opening polymerization of ε‐caprolactone substituted by various functional groups, protected if needed, in α‐ or γ‐position. In a second strategy, the functional groups are grafted onto preformed polyesters chains in α‐position of the carbonyl groups. α‐chloro‐ε‐caprolactone is quite an interesting monomer because, after polymerization, the activated chloride can be easily derivatized by atom transfer radical addition and “click” chemistry, respectively. Similarly, γ‐acrylic‐ε‐caprolactone is precursor of (co)polyesters well‐suited to derivatization of the pendent double bonds by Michael addition.