Transformation of Thioester‐Initiated Star Polymers into Linear Arms via Native Chemical Ligation

The synthesis of a new class of Cu-mediated polymerization initiators with thioester functionality is demonstrated and their polymerization kinetics via single-electron transfer living radical polymerization is reported. From periodic sampling, it is found that thioester- or ester-based initiators can be employed interchangeably, resulting in very similar polymerization rates. Furthermore, a multifunctional thioester initiator is employed for the preparation of a well-defined four-arm star-shaped polymer. It is further shown that the full dissociation of the star polymer into linear arms via native chemical ligation can easily be followed via size exclusion chromatography, as a result of the change in hydrodynamic volume. Finally, the obtained linear polymers are characterized via matrix-assisted laser desorption/ionization-time of flight mass spectrometry and found to be in good agreement with the expected molecular weight distribution that confirms the successful transformation.