• click chemistry;
  • dendrimers;
  • methyl acrylate;
  • radical polymerization;


The development of a novel nucleophilic thio-bromo “Click” reaction, specifically base-mediated thioetherification of thioglycerol with α-bromoesters was reported in an earlier article. The combination of this thio-bromo click reaction with subsequent acylation with 2-bromopropionyl bromide provides an iterative two-step divergent growth approach to the synthesis of a new class of poly(thioglycerol-2- propionate) (PTP) dendrimers. In this article, the addition of a third step, the single-electron transfer living radical polymerization (SET-LRP) of methyl acrylate (MA), was shown to provides access to a three-step “branch” and “grow” divergent approach to dendritic macromolecules wherein poly(methyl acrylate) (PMA) connects the branching subunits. This facile methodology can provide a diversity of dendritic macromolecular topologies and will ultimately provide the means to the development of self-organizable dendritic macromolecules. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3940–3948, 2009