Abstract
This article reviews the various methods developed to generate di- and multicarbanionic lithiated initiators, the difficulties associated with their synthesis but also their potential in macromolecular engineering. It is shown that a wealth of complex macromolecular architectures based on monomers amenable to carbanionic polymerization can now be synthesized by divergent approach from these di- and multicarbanionic lithiated initiators. A comparison is made with other types of multifunctional initiators that have been developed from other living/controlled polymerizations, generating similar complex polymeric architectures from other monomers. A comparison is also made with the structures generated by the convergent carbanionic approach.