Our laboratory has reported the elaboration of an iterative strategy for the synthesis of dendritic macromolecules from conventional monomers. This synthetic method involves a combination of self-regulated metal-catalyzed living radical polymerization initiated from arenesulfonyl chlorides and an irreversible terminator multifunctional initiator (TERMINI). The previous TERMINI, (1,1-dimethylethyl)[[1[3,5-bis(S-phenyl-4-N,N' diethylthiocarbamate)phenyl]ethenyl]oxy]dimethylsilane, was prepared in nine reaction steps. The replacement of the previous TERMINI with one that requires only three steps for its synthesis, diethylthiocarbamic acid S-{3-[1-tertbutyl-dimethyl-silanyloxy)-vinyl]-5-diethylcarbamoylsulfanyl -phenyl} ester, and the use of the more reactive Cu2S/2,2'-bipyridine rather than the Cu2O/2,2'-bipyridine self-regulated catalyst have generated an accelerated method for the synthesis of dendritic macromolecules. This method provides rational design strategies for the synthesis of dendritic macromolecules with different compaction by the use of a single monomer. (c) 2005 Wiley Periodicals, Inc.