Comparing different initiator types for Cu‐mediated polymerization has shown that thioester‐based initiators can be an excellent alternative that allow further conjugation via native chemical ligation, as exemplified on a star polymer using l‐cysteine methyl ester hydrochloride. Abstract 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...
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