Stereoselective photoredox ring-opening polymerization of O-carboxyanhydrides

Biodegradable polyesters with various tacticities have been synthesized by means of stereoselective ring-opening polymerization of racemic lactide and β-lactones but with limited side-chain groups. However, stereoselective synthesis of functional polyesters remains challenging from O-carboxyanhydrides that have abundant pendant side-chain functional groups. Herein we report a powerful strategy to synthesize stereoblock polyesters by stereoselective ring-opening polymerization of racemic O-carboxyanhydrides with the use of photoredox Ni/Ir catalysts and a selected Zn complex with an achiral ligand. The obtained stereoblock copolymers are highly isotactic with high molecular weights (> 70 kDa) and narrow molecular weight distributions (M _w/M _n < 1.1), and they display distinct melting temperatures that are similar to their stereocomplex counterparts. Furthermore, in one-pot photoredox copolymerization of two different O-carboxyanhydrides, the use of such Zn complex mediates kinetic resolution of the comonomers during enchainment and shows a chirality preference that allows for the synthesis of gradient copolymers.